Toward well-defined colloidal particles: Efficient fractionation of lignin by a multi-solvent strategy.

Colloidal lignin particles (CLPs) have sparked various intriguing insights toward bio-polymeric materials and triggered many lignin-featured innovative applications. Here, we report a multi-solvent sequential fractionation methodology integrating green solvents of acetone, 1-butanol, and ethanol to fractionate industrial lignin for CLPs fabrication. Through a rationally designed fractionation strategy, multigrade lignin fractions with variable hydroxyl group contents, molecular weights, and high purity were obtained without altering their original chemical structures. CLPs with well-defined morphology, narrow size distribution, excellent thermal stability, and long-term colloidal stability can be obtained by rational selection of lignin fractions. We further elucidated that trace elements (S, N) were reorganized onto the near-surface area of CLPs from lignin fractions during the formation process in the form of -SO42- and -NH2. This work provides a sustainable and efficient strategy for refining industrial lignin into high-quality fractions and an in-depth insight into the CLPs formation process, holding great promise for enriching the existing libraries of colloidal materials.

Direct ink writing with high-strength and swelling-resistant biocompatible physically crosslinked hydrogels.

The three-dimensional (3D) printing of hydrogels has great potential for biomedicine applications. However, it is very rare to find suitable printable materials with high strength and swelling resistance that can offer high performance. To address this challenge, this paper demonstrates the fabrication of tailored hydrogel structures by using the direct ink writing (DIW) of hybrid hydrogel inks (polyvinyl alcohol (PVA) and κ-carrageenan) with outstanding rheology. The freezing and thawing processes following DIW induce the formation of physically crosslinked networks due to the crystallinity of PVA, and thus enhance the mechanical properties and swelling resistance of the printed architectures. The resultant hydrogels exhibit excellent cytocompatibility, and most importantly, cells not only attach well to the surface of the hydrogels, but also stretch into the spaces in the grid architectures, providing appropriate microenvironments for cell culture. The physically crosslinked hydrogels, with high strength, outstanding swelling resistance, biocompatibility, and good compatibility with the DIW technique, offer many opportunities in fields such as tissue engineering, drug delivery, bone regeneration and implant medicine.

Fractionation of alkali lignin by organic solvents for biodegradable microsphere through self-assembly.

Here we report a centrifugation-based fractionation methodology that was integrated with three types of organic solvents to fractionate industrial alkali lignin toward the fabrication of lignin microsphere. The Fourier-transform infrared spectroscopy (FT-IR) result showed that the chemical structure of lignin was not changed by solvent fractionation. Soluble lignin in each solvent had lower molecular weight, improved polydispersity index (PDI) and less impurities (S, N), while insoluble lignin had a high bio-char yield and can be utilized as potential carbon source for porous carbon nanosphere materials. In addition, well-shaped lignin microsphere with smooth or anisotropic surface can be prepared by selecting proper lignin fraction without any chemical modification. This work thus provides a new strategy for the derivation of lignin as raw materials for value-added products, which paved a new way to develop a green and sustainable bio-refining industry.

Preparation and characterization of thermo-sensitive gel with phenolated alkali lignin.

Thermo-sensitive gel exhibits great potential industrial application. It has been widely used in tissue repair, drug release and water purification for its property of phase transition in response to external stimuli, reusability and biocompatibility. In this study, a novel lignin-based thermo-sensitive gel was synthesized with alkali lignin by two steps. Firstly, phenolated lignin (PPAL) was synthesized with purified alkali lignin (PAL) catalyzed by sulfuric acid. Subsequently, thermo-sensitive gel was achieved by thermal polymerization of phenolated alkali lignin and N-isopropylacrylamide (NIPAAm). Furthermore, the prepared hydrogels were characterized in terms of thermal behavior, interior morphology and their swelling behavior. Compared with PAL-based gel, the obtained PPAL-based gel exhibits a higher crosslinking density and lower critical solution temperature (LCST) due to the increase of reaction site and smaller space volume of the hydrophobic side groups grafted on NIPAAm. TGA data revealed that thermal stability of gel was enhanced (50% weight loss at ~380 °C) by using lignin as precursor. SEM images showed that a more regular interior morphology, better compressive strength was also found (PPAL0.05, 11.15 KPa). Furthermore, the swelling ratio of PPAL-based gel was lower than that of PAL-based gel due to its more complex structure.