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![Sketch model for typical softwood tracheid and hardwood fibers cells. Reproduced with permission.[²²] Copyright 1968, Springer Nature.](publication/344317483/figure/fig12/AS:11431281173306742@1688829599249/Sketch-model-for-typical-softwood-tracheid-and-hardwood-fibers-cells-Reproduced-with.png)
Sketch model for typical softwood tracheid and hardwood fibers cells. Reproduced with permission.[²²] Copyright 1968, Springer Nature.
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Plant biomass, especially wood, has been used for structural materials since ancient times. It is also showing great potential for new structural materials and it is the major feedstock for the emerging biorefineries for building a sustainable society. The plant cell wall is a hierarchical matrix of mainly cellulose, hemicellulose, and lignin. Here...
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The purification of hydroxycinnamic acids [p-coumaric acid (pCA) and ferulic acid (FA)] from grass cell walls requires high-cost processes. Feedstocks with increased levels of one hydroxycinnamate in preference to the other are therefore highly desirable. We identified and conducted expression analysis for nine BAHD acyltransferase ScAts genes from...
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... Hemicellulose is a heteropolymer composed of several monosaccharides and is linked to cellulose through hydrogen bonding and lignin through covalent bonding, respectively [29]. Lignin, which consists of coniferyl alcohol, sinapyl alcohol, and p-coumaryl alcohol, improves cell wall strength by filling the space between cellulose and hemicellulose and combining the lignocellulose matrix [30]. The relationship among the three is shown in Figure 3b [32]. ...
Liquefaction conversion technology has become one of the hottest biomass conversion methods due to its flexible material selection and extensive product applications. Exploring biomass liquefaction conversion focuses on catalysts, biomass/water ratio, and reaction temperature. However, it is found that solvents are crucial in the biomass liquefaction process and significantly impact the type of liquefied products and bio-oil yield. Given the current rapid development trend, timely sorting and summary of the solvent effect in the biomass liquefaction process can promote the subsequent development and industrialization of more efficient and cleaner biomass liquefaction technology. Therefore, this review first introduces the characteristics of water as the liquefaction solvent, then summarizes the effects of organic solvents on liquefaction, and finally elaborates on the synergistic effect of co-solvents, which provides a more systematic overview of solvent effects in the liquefaction process. Meanwhile, prospects are put forward for the future development of biomass liquefaction conversion.
... Several molecular models of cell wall constituents have been built in order to explain the mechanical behaviors of wood and bamboo composites [51][52][53][54][55]. An accurate forcefield is crucial for obtaining realistic molecular motions; numerous forcefields have been developed to describe different material systems [56]. To comprehend the origin of the anisotropic features of bamboo fiber, distinct molecular models representing the three cell wall constituents, namely cellulose, hemicellulose, and lignin, have been developed [53]. ...
As a result of global sustainable development, natural fiber composites (NFCs) have become increasingly attractive due to their remarkable performance, novel functionality, and eco-friendliness. Natural fibers are biodegradable, affordable, and low-density, which makes them potential materials for use in developing alternatives to traditional petroleum-based synthetic fiber composites. However, challenges such as inadequate compatibility between natural fibers and matrix limit the further development of NFCs. Studies have shown that molecular dynamics (MD) simulations can offer valuable insights into the fundamental properties and deformation mechanisms governing the macroscopic performances of NFCs, including mechanical properties, thermal stability, and interfacial interactions. Based on the underlying understanding of the nanostructure of natural fibers, these fibers can be modified at nanoscale to improve the performance of NFCs. This paper first reviews the hierarchical structures of natural fibers, mainly wood and bamboo fibers, highlighting their relationship with mechanical and thermal properties. Treatments to improve natural fiber-matrix compatibilities are then presented. The fundamental factors behind the functionalized properties of modified NFCs are emphasized from the nanoscale. Additionally, applications of NFCs as structural and functional materials in the construction, automotive, and aerospace industries are reviewed. Finally, this paper identifies the growing use of machine learning-assisted MD simulation techniques to facilitate the design of NFCs. Literature and data sources for this study were obtained through a combination of online academic databases, citation chaining, government databases, and industry reports.
... INTRODUCTION distributed and abundant homoglycan (Matthews et al. 2006;Zhao et al. 2013;Zhang et al. 2019;Zhou et al. 2021). ...
... For cellulose I, hydrogen bonding within the cellulose chains allows a linear arrangement of cellulose, and two adjacent cellulose chains are bound together mainly by hydrogen bonding, forming cellulose sheets. Stacked sheets, conversely, are thought to have no hydrogen bonding interactions between them but rather form cellulose microfibril crystals through van der Waals interactions (Zhou et al. 2021). Notably, the orientation of the C6 hydroxymethyl group will highly affect the hydrogen bonding and chain conformation. ...
... The interaction between cellulose microfibrils and solvents or the solubilization process of cellulose microfibrils is a research hotspot (Zhang et al. 2019;Zhou et al. 2021). ...
The structural changes of cellulose in non-solvent liquid media can provide insights into the high-value utilization of cellulose. This study includes molecular dynamics simulations of 36-chain cellulose Iβ microfibril model (Iβ-MF) behavior in 16 non-solvent liquids with different polarities at room temperature using two carbohydrate force fields (CHARMM36, GLYCAM06). Iβ-MF in CHARMM36 retains more than 70% of the tg conformation in 16 liquids, and the retention of the tg conformation increased with decreasing liquid polarity. Liquid polarity can affect the hydroxymethyl conformation of cellulose, which is only an appearance, and the real driving force behind is the electrostatic interaction between liquid molecules and cellulose. Furthermore, changing the 1,4 electrostatic scaling factor of GLYCAM06 can effectively affect the structural convergence of Iβ-MF. The Iβ-MF forms an alternating layer structure in the gg/gt conformation in a medium to high polarity non-solvent liquid, while the model undergoes untwisting. Model untwisting is inextricably linked to the degree of alternate layer structure formation. This paper provides a theoretical basis for the molecular study of nanocellulose structures from an energy-structure-property perspective.
... Many hierarchical material architectures are found in biological materials (1)(2)(3)(4)(5), such as in bone (2,6,7), wood (8), sea sponges and diatoms (9)(10)(11)(12)(13), honeycomb structures (14)(15)(16), and various spider webs (17)(18)(19)(20)(21)(22)(23)(24)(25)(26)(27)(28). Like all biological structures, spider webs have been well adapted to their natural environments over hundreds of millions of years of evolution (29,30) and a diversity of web structures exist across spider species. ...
Spider webs are incredible biological structures, comprising thin but strong silk filament and arranged into complex hierarchical architectures with striking mechanical properties (e.g., lightweight but high strength, achieving diverse mechanical responses). While simple 2D orb webs can easily be mimicked, the modeling and synthesis of 3D-based web structures remain challenging, partly due to the rich set of design features. Here, we provide a detailed analysis of the heterogeneous graph structures of spider webs and use deep learning as a way to model and then synthesize artificial, bioinspired 3D web structures. The generative models are conditioned based on key geometric parameters (including average edge length, number of nodes, average node degree, and others). To identify graph construction principles, we use inductive representation sampling of large experimentally determined spider web graphs, to yield a dataset that is used to train three conditional generative models: 1) an analog diffusion model inspired by nonequilibrium thermodynamics, with sparse neighbor representation; 2) a discrete diffusion model with full neighbor representation; and 3) an autoregressive transformer architecture with full neighbor representation. All three models are scalable, produce complex, de novo bioinspired spider web mimics, and successfully construct graphs that meet the design objectives. We further propose an algorithm that assembles web samples produced by the generative models into larger-scale structures based on a series of geometric design targets, including helical and parametric shapes, mimicking, and extending natural design principles toward integration with diverging engineering objectives. Several webs are manufactured using 3D printing and tested to assess mechanical properties.
... In nature, lignin is a polyphenolic polymer made up of random linkages that associate with cellulose and hemicellulose [5] and functions as a protective barrier by making biomass resistant to microorganisms and hence, disease. Lignin also greatly enhances the mechanical strength of biomass [6,7]. ...
Despite lignin’s global abundance and its use in biomedical studies, our understanding of how lignin regulates disease through modulation of cell morphology and associated phenotype of human cells is unknown. We combined an automated high-throughput image cell segmentation technique for quantitatively measuring a panel of cell shape descriptors, droplet digital Polymerase Chain Reaction for absolute quantification of gene expression and multivariate data analyses to determine whether lignin could therapeutically modulate the cell morphology and phenotype of inflamed, degenerating diseased human cells (osteoarthritic (OA) chondrocytes) towards a healthier cell morphology and phenotype. Lignin dose-dependently modified all aspects of cell morphology and ameliorated the diseased shape of OA chondrocytes by inducing a less fibroblastic healthier cell shape, which correlated with the downregulation of collagen 1A2 (COL1A2, a major fibrosis-inducing gene), upregulation of collagen 2A1 (COL2A1, a healthy extracellular matrix-inducing gene) and downregulation of interleukin-6 (IL-6, a chronic inflammatory cytokine). This is the first study to show that lignin can therapeutically target cell morphology and change a diseased cells’ function towards a healthier cell shape and phenotype. This opens up novel opportunities for exploiting lignin in modulation of disease, tissue degeneration, fibrosis, inflammation and regenerative medical implants for therapeutically targeting cell function and outcome.
... Lignocellulose struc-ture has been simulated using theoretical approaches ranging over multiple scales, the classification of which has been well described in the comprehensive review by Ciesielski et al. [6]. At the lowest scale, these models can simulate processes as diverse as: pyrolysis [7,8], the detailed structure and properties of lignocellulosic biomass [9], enzyme mechanisms [10,11], and the effects of lignin binding on cellulose and cellulase enzymes [12]. The typically used methods for such detailed models are Density Functional Theory (DFT) and Molecular Dynamics (MD). ...
Enzymatic digestion of lignocellulosic plant biomass is a key step in bio-refinery approaches for the production of biofuels and other valuable chemicals. However, the recalcitrance of this material in conjunction with its variability and heterogeneity strongly hampers the economic viability and profitability of biofuel production. To complement both academic and industrial experimental research in the field, we designed an advanced web application that encapsulates our in-house developed complex biophysical model of enzy-matic plant cell wall degradation. PREDIG (https://predig.cs.hhu.de/) is a user-friendly, free, and fully open-source web application that allows the user to perform in silico experiments. Specifically, it uses a Gillespie algorithm to run stochastic simulations of the enzymatic saccharification of a lignocellulose microfibril, at the mesoscale, in three dimensions. Such simulations can for instance be used to test the action of distinct enzyme cocktails on the substrate. Additionally, PREDIG can fit the model parameters to uploaded experimental time-course data, thereby returning values that are intrinsically difficult to measure experimentally. This gives the user the possibility to learn which factors quantitatively explain the recalcitrance to saccharification of their specific biomass material.
... Small molecules can easily pass through the amorphous region due to the enormous inter-molecular gap [23]. The interaction between silicone oil molecules and cellulose tends to take place in the amorphous region of cellulose. ...
The impact of combined oil and thermal modification on the properties of bamboo was explored through macroscopic tests, but the internal mechanism remaine4d challenging to comprehend. To gain further insights, this research employed molecular dynamics simulation to estimate the mechanical properties, diffusion coefficient, cohesive energy density, and chain flexibility of bamboo fibers following oil heat treatment. A model of oil-cellulose composite was established and simulated at varying temperatures. Results showed that oil heat treatment led to higher mechanical strength and modulus of elasticity in bamboo fibers compared to untreated ones. Additionally, the increase in diffusion coefficient and cohesive energy density, as well as the optimization of cellulose chain flexibility, indicated an improvement in the fiber characteristics. Of note, the most significant enhancement in the mechanical properties of cellulose and the utilization rate of bamboo was observed after oil heat treatment at 180℃.
... Specifically, developments in molecular modeling methods such as MD and quantum mechanical density functional theory (DFT) have been instrumental for this advancement and has recently been reviewed by Bergenstråhle-Wohlert and Brady, 953 Zhang et al., 954 and by Buehler and coworkers. 955 While MD is based on classical physics and treats atoms as point particles that are interacting pairwise through empirical potentials, DFT takes the electronic configuration into account and is therefore considered very close to an ab initio method. This has consequences for its practical use. ...
Modern technology has enabled the isolation of nanocellulose from plant-based fibers, and the current trend focuses on utilizing nanocellulose in a broad range of sustainable materials applications. Water is generally seen as a detrimental component when in contact with nanocellulose-based materials, just like it is harmful for traditional cellulosic materials such as paper or cardboard. However, water is an integral component in plants, and many applications of nanocellulose already accept the presence of water or make use of it. This review gives a comprehensive account of nanocellulose-water interactions and their repercussions in all key areas of contemporary research: fundamental physical chemistry, chemical modification of nanocellulose, materials applications, and analytical methods to map the water interactions and the effect of water on a nanocellulose matrix.
... 74 For example, the high axial modulus and fiber strengths of cellulose are usually attributed to hydrogen bonding, while neglecting the concept of molecular dynamics. 74,75 Another example is the argument on the physical dynamics of cellulose dissolution mechanisms and the insolubility in water, which are widely accepted that hydrogen bonds play a significant role in these; however, this is unlikely as the contribution of hydrogen bonds to cellulose insolubility, for example, is negligible and lesser than the hydrophobic solvation energy (ΔG vdw ). 74,76 Because factors such as molecular geometry, multibody interactions of neighboring atoms, the shape of molecular interfaces, and slight changes in water density surrounding a cellulose molecule all contribute to the chemistry of hydrophobic solvation. ...
Envisage a world where discarded electrical/electronic devices and single-use consumables can dematerialize and lapse into the environment after the end-of-useful life without constituting health and environmental burdens. As available resources are consumed and human activities build up wastes, there is an urgency for the consolidation of efforts and strategies in meeting current materials needs while assuaging the concomitant negative impacts of conventional materials exploration, usage, and disposal. Hence, the emerging field of transient technology (Green Technology), rooted in eco-design and closing the material loop toward a friendlier and sustainable materials system, holds enormous possibilities for assuaging current challenges in materials usage and disposability. The core requirements for transient materials are anchored on meeting multicomponent functionality, low-cost production, simplicity in disposability, flexibility in materials fabrication and design, biodegradability, biocompatibility, and environmental benignity. In this regard, biorenewables such as cellulose-based materials have demonstrated capacity as promising platforms to fabricate scalable, renewable, greener, and efficient materials and devices such as membranes, sensors, display units (for example, OLEDs), and so on. This work critically reviews the recent progress of nanocellulosic materials in transient technologies toward mitigating current environmental challenges resulting from traditional material exploration, usage, and disposal. While spotlighting important fundamental properties and functions in the material selection toward practicability and identifying current difficulties, we propose crucial research directions in advancing transient technology and cellulose-based materials in closing the loop for conventional materials and sustainability.
... There exist constraints to developing such a framework mainly because of the limitations on the existing computational capabilities. 151,152 Novel computational techniques such as machine learning (ML) aided materials discovery 153-160 might provide another avenue to accelerate materials design by various intermolecular bonding strategies. For example, hydrogen bond donor and acceptor strengths 161 in chloroform (CCl 4 ) were determined using ML methods with values quite close to experiments, typically done using infrared spectroscopy techniques. ...
Conventional strategies for materials design have long been used by leveraging primary bonding, such as covalent, ionic, and metallic bonds, between constituent atoms. However, bond energy required to break primary bonds is high. Therefore, high temperatures and enormous energy consumption are often required in processing and manufacturing such materials. On the contrary, intermolecular bonds (hydrogen bonds, van der Waals forces, electrostatic interactions, imine bonds, etc.) formed between different molecules and functional groups are relatively weaker than primary bonds. They, thus, require less energy to break and reform. Moreover, intermolecular bonds can form at considerably longer bond lengths between two groups with no constraint on a specific bond angle between them, a feature that primary bonds lack. These features motivate unconventional strategies for the material design by tuning the intermolecular bonding between constituent atoms or groups to achieve superior physical properties. This paper reviews recent development in such strategies that utilize intermolecular bonding and analyzes how such design strategies lead to enhanced thermal stability and mechanical properties of the resulting materials. The applications of the materials designed and fabricated by tuning the intermolecular bonding are also summarized, along with major challenges that remain and future perspectives that call for further attention to maximize the potential of programming material properties by tuning intermolecular bonding.
