Atomistic Simulations of Polydisperse Lignin Melts Using Simple Polydisperse Residue Input Generator.

Understanding the physics of lignin will help rationalize its function in plant cell walls as well as aiding practical applications such as deriving biofuels and bioproducts. Here, we present SPRIG (Simple Polydisperse Residue Input Generator), a program for generating atomic-detail models of random polydisperse lignin copolymer melts i.e., the state most commonly found in nature. Using these models, we use all-atom molecular dynamics (MD) simulations to investigate the conformational and dynamic properties of polydisperse melts representative of switchgrass (Panicum virgatum L.) lignin. Polydispersity, branching and monolignol sequence are found to not affect the calculated glass transition temperature, Tg. The Flory-Huggins scaling parameter for the segmental radius of gyration is 0.42 ± 0.02, indicating that the chains exhibit statistics that lie between a globular chain and an ideal Gaussian chain. Below Tg the atomic mean squared displacements are independent of molecular weight. In contrast, above Tg, they decrease with increasing molecular weight. Therefore, a monodisperse lignin melt is a good approximation to this polydisperse lignin when only static properties are probed, whereas the molecular weight distribution needs to be considered while analyzing lignin dynamics.

Cross-Linked Nanocellulosic Materials and Their Applications.

Nanocelluloses (NCs) have remarkable mechanical properties and contain abundant surface functional groups that can be modified or cross-linked with other materials. They have been widely used as an environment-friendly reinforcing agent in polymer composites. However, for applications that are carried out in humid environments or aqueous suspensions, hydrophilicity of NCs lower their mechanical integrity. Hence, cross-linking techniques have been investigated in recent years for preparing NC-based materials that are dimensionally stable under humid or aqueous environments and have better physicochemical properties. This Minireview examines the quickly growing field of cross-linked NC-based materials, which have many benefits including improved aqueous, structural, mechanical, and thermal stability. In addition, the potential application of cross-linked NC-based materials in adsorption of heavy metal is discussed.

Chemically Cross-Linked Cellulose Nanocrystal Aerogels for Effective Removal of Cation Dye.

In this study, porous aerogels were prepared by directional freeze-drying via cross-linking cellulose nanocrystals (CNCs) with poly(methyl vinyl ether-co-maleic acid) (PMVEMA) and poly(ethylene glycol) (PEG). The thermal properties and physical adsorption performance toward cation methylene blue dye of the obtained CNC aerogels were investigated. The maximum degradation temperature was increased from 324°C of CNCs to 355°C of cross-linked CNC aerogels. The dye adsorption isotherm results showed that the maximum methylene blue adsorption capacity of CNC aerogels was 116.2 mg g-1, according to the Langmuir model, which was mainly due to the electrostatic attractions between negatively charged carboxyl groups or sulfonate groups on the CNC aerogles and cation MB molecules. The reusability test showed that the CNC aerogels contained the same dye adsorption performance in five adsorption/desorption cycles. Overall, this study described an ideal alternative for water purification with high dye adsorption capacity and enhanced physical performance.

Cross-linked poly(methyl vinyl ether-co-maleic acid)/poly(ethylene glycol)/nanocellulosics foams via directional freezing.

Aligned micro- and nanoporous materials have gained tremendous interest since they provide great potential in organic electronics, absorbents, biomedicine and tissue engineering. Herein, cellulose nanofibrils (CNFs) and cellulose nanocrystals (CNCs) cross-linked with poly(methyl vinyl ether-co-maleic acid) (PMVEMA) and poly(ethylene glycol) (PEG) foams were prepared by both the directional and un-directional freezing techniques. Aligned three-dimensional porous structures were observed for the directional frozen foams after lyophilization via scanning electron microscope (SEM). As a result, these highly organized structures exhibited enhanced mechanical performance properties. Particularly, for the 25% CNF foams, the compression modulus increased 60% compared with the un-directional frozen samples. These nanocellulosics-based foams could absorb up to 10-fold water of their initial weight with excellent water stability when immersed in water for more than 48 h. Overall, this study describes a novel process combining cross-linking and directional freezing which successfully fabricates naturally derived foams with anisotropic structure.

Biomimetic composite scaffold from an in situ hydroxyapatite coating on cellulose nanocrystals.

A novel nanocomposite scaffold was developed by homogeneous deposition of hydroxyapatite (HAP) on a cellulose nanocrystals (CNCs) matrix suspended in a simulated body fluid (SBF). By adjusting the pH of the SBF, the HAP content in the nanocomposite could be controlled between 15 wt% and 47 wt%. Physical and chemical characteristics of the nanocomposites were analyzed by SEM, FTIR, XRD, SAED, and TEM, which confirmed the successful incorporation of HAP onto the CNCs. The nanocomposites were then freeze-casted into porous scaffolds by different solidification technologies (i.e., directional freezing (DF), plunging in liquid N2 (PL) or in a -20 °C freezer (FZ)) followed by lyophilization. Compression testing of the HAP/CNCs foams indicated that DF caused significant improvement in mechanical properties due to the specific orientation and anisotropic porous structure compared to conventional freezing methods such as PL and FZ. Moreover, the scaffold with high HAP content exhibited improved mechanical and thermal properties, which holds potential for application in bone tissue engineering.