Towards Photocrosslinkable Lyotropic Blends of Organosolv Lignin and Hydroxypropyl Cellulose for 3D Printing by Direct Ink Writing.

Polymer blends containing up to 70% organosolv lignin content and lyotropic cellulose derivatives have been established as "lignin inks" for direct ink writing of fully biobased 3D parts. However, a fast-crosslinking mechanism is needed to improve throughput and design space. In this paper, UV-photocrosslinkable organosolv lignin/hydroxypropyl cellulose inks are formulated through doping with common photocrosslinkers.

Characterization and In Vitro Cytotoxicity Safety Screening of Fractionated Organosolv Lignin on Diverse Primary Human Cell Types Commonly Used in Tissue Engineering.

There is limited data assessing the cytotoxic effects of organosolv lignin with cells commonly used in tissue engineering. Structural and physico-chemical characterization of fractionated organosolv lignin showed that a decrease of the molecular weight (MW) is accompanied by a less branched conformation of the phenolic biopolymer (higher S/G ratio) and an increased number of aliphatic hydroxyl functionalities. Enabling stronger polymer-solvent interactions, as proven by the Hansen solubility parameter analysis, low MW organosolv lignin (2543 g/mol) is considered to be compatible with common biomaterials.

Direct Ink Writing of Fully Bio-Based Liquid Crystalline Lignin/Hydroxypropyl Cellulose Aqueous Inks: Optimization of Formulations and Printing Parameters.

Following the recent demonstration of the potential to direct ink write lyotropic blends of organosolv lignin (OSL) and hydroxypropyl cellulose (HPC), this study aims to optimize the formulations and direct ink writing parameters for fully bio-based lignin/HPC inks. A prescreening identifies the theoretical window of printability for different compositions for formulations based on OSL solutions of 45, 47.5, and 50% solid contents and OSL/HPC wt %/wt % ratios of 30/70, 40/60, and 50/50.

Grafting Diels-Alder moieties on cellulose nanocrystals through carbamation.

The Diels-Alder reaction is a promising click chemistry for the design of advanced materials from cellulose nanocrystals (CNCs). Transferring such chemistry to cellulose nanocrystals requires the precise grafting of reactive Diels-Alder moeities under heterogeneous conditions without compromising the nanocrystals morphology. In this study toluene diisocyanate is used as a spacer to graft Diels-Alder moieties viz the furyl and protected maleimido moieties onto cellulose nanocrystals.

Lignin in Bio-Based Liquid Crystalline Network Material with Potential for Direct Ink Writing.

The flow-induced supramolecular arrangement, or band texture, present in water-soluble anisotropic films prepared from blend solutions of hydroxypropyl cellulose and organosolv lignin is locked via esterification with bio-based polycarboxylic acids. Subsequent to shear casting of the blend solutions, the chemical cross-linking with citric acid-based cross-linkers and a dimerized fatty acid yields water-insoluble, anisotropic films prone to swelling in water. The liquid crystalline networks are analyzed by means of polarized optical microscopy, tensile testing, Fourier transform infrared, and swelling experiments.

Lignin-Assisted Stabilization of an Oriented Liquid Crystalline Cellulosic Mesophase, Part B: Toward the Molecular Origin and Mechanism.

Lignin valorization has been scarcely considered in the form of liquid crystalline polymer blends. Recently, a stabilizing effect of organosolv lignin (OSL) on the oriented mesophase of hydroxypropyl cellulose (HPC) was observed and related to drastic improvements in tensile properties of the blends. With a view to elucidating this relaxation phenomenon, different molecular weight fractions and derivatives of organosolv lignin are synthesized, blended in solution with the liquid crystalline cellulosic polymer and analyzed in regard to their effect on the microstructural evolution of shear-aligned HPC chains.

Lignin-Assisted Stabilization of an Oriented Liquid Crystalline Cellulosic Mesophase, Part A: Observation of Microstructural and Mechanical Behavior.

Liquid crystalline polymer blends containing lignin have been scarcely studied in the literature, albeit demonstrating potential for the design of high-performance lignin-based materials. In this study, organosolv lignin is blended in solution with hydroxypropyl cellulose (HPC), a lyotropic cellulose derivative, and its impact on the dynamics of the cellulosic liquid crystalline mesophase is investigated. Rheological measurements and rheo-optical investigations under crossed polarizers reveal that lignin enhances the persistence of the shear-induced orientation of the cellulosic macromolecules.

Thermodynamic and Kinetic Study of Diels-Alder Reaction between Furfuryl Alcohol and -Hydroxymaleimides-An Assessment for Materials Application.

The study of Diels-Alder reactions in materials science is of increasing interest. The main reason for that is the potential thermoreversibility of the reaction. Aiming to predict the behavior of a material modified with maleimido and furyl moieties, H NMR and UV-Vis solution studies of the Diels-Alder reaction between furfuryl alcohol and two -hydroxymaleimides are explored in the present study.

Acetyl Groups in : Fate of Acetates during Organosolv and Ionosolv Pulping.

During biomass fractionation, any native acetylation of lignin and heteropolysaccharide may affect the process and the resulting lignin structure. In this study, (TC) and its lignin isolated by milling (MWL), ionosolv (ILL) and organosolv (EOL) methods were investigated for acetyl group content using FT-Raman, ¹H NMR, 2D-NMR, back-titration, and Zemplén transesterification analytical methods. The study revealed that TC is a highly acetylated grass; extractive free TC (TC) and TC MWL exhibited similar values of acetyl content: 6 wt % and 8 wt % by Zemplén transesterification, respectively, and 11 wt % by back-titration.

Imidazole, a New Tunable Reagent for Producing Nanocellulose, Part I: Xylan-Coated CNCs and CNFs.

Imidazole is reported to be an effective reactant for the production of nanocellulose from hardwood pulp. The morphologies and surface properties of the nanocellulose can be simply tailored according to the water content in the imidazole system: with pure imidazole, cellulose nanofibrils (CNFs) in a yield of 10 wt % can be produced. With 25 wt % of water in imidazole, cellulose nanocrystals (CNCs) are obtained in 20 wt % yield.

Preparation and Chemical/Microstructural Characterization of Azacrown Ether-Crosslinked Chitosan Films.

Chemically stable porous azacrown ether-crosslinked chitosan films were prepared by reacting varying molar amounts of N,N-diallyl-7,16-diaza-1,4,10,13-tetraoxa-dibenzo-18-crown-6 (molar equivalents ranging from 0, 0.125, 0.167, 0.

Swelling and hydrolysis kinetics of Kraft pulp fibers in aqueous 1-butyl-3-methylimidazolium hydrogen sulfate solutions.

1Butyl-3-methylimidazolium hydrogen sulfate ([Bmim]HSO4) is efficient at extracting cellulose nanocrystals from pulp fibers. To shed some light on the respective contributions of swelling and hydrolysis of pulp fibers by [Bmim]HSO4, the physical, structural and morphological characteristics of hardwood Kraft pulp fibers were monitored under various conditions of temperature, water content and time. Swelling was largely compounded by hydrolysis at the highest temperatures (120°C) as evidenced by mass loss and reduced degree of polymerization (DPn) at this temperature.

Synthesis and Characterization of Macrocyclic Polyether N,N'-Diallyl-7,16-diaza-1,4,10,13-tetraoxa-dibenzo-18-crown-6.

In this study an efficient and direct production procedure for a macrocyclic polyether N,N'-diallyl-7,16-diaza-1,4,10,13-tetraoxa-dibenzo-18-crown-6 from the reaction of catechol and N,N-bis(2-chloroethyl)prop-2-en-1-amine in n-butanol in the presence of a strong base is reported. The synthesis involves a two-step addition of sodium hydroxide to enhance the cyclization process, and at the end of the reaction, the reaction mixture is neutralized and the solvent replaced with water in-situ through distillation to afford a relatively pure precipitate that is easily recrystallized from acetone. The yield of the macrocycle was 36%-45% and could be scaled-up to one-mole quantities.

Ionic liquid-mediated technology to produce cellulose nanocrystals directly from wood.

We report for the first time the direct extraction of cellulose nanocrystals (CNCs) from wood by means of a 1-ethyl-3-methylimidazolium acetate ([EMIM][OAc]) treatment. A native cellulosic product could be recovered in 44% yield with respect to wood cellulose content. The product was analyzed for morphological (TEM, AFM, XRD), chemical (FTIR, (13)C CP/MAS NMR), thermal (DSC, TGA) and surface properties (Zeta potential, contact angle).

Role of Cellulose Nanocrystals on the Microstructure of Maleic Anhydride Plasma Polymer Thin Films.

Recently, it was shown that the microstructure of a maleic anhydride plasma polymer (MAPP) could be tailored ab initio by adjusting the plasma process parameters. In this work, we aim to investigate the ability of cellulose nanocrystals (CNCs) to induce topographical structuration. Thus, a new approach was designed based on the deposition of MAPP on CNCs model surfaces.

Cellulose nanocrystals' production in near theoretical yields by 1-butyl-3-methylimidazolium hydrogen sulfate ([Bmim]HSO4)-mediated hydrolysis.

We report on near theoretical yield production of cellulose I nanocrystals (CNCs) using a two-step hydrolysis with the mildly acidic ionic liquid (IL) 1-butyl-3-methylimidazolium hydrogen sulfate ([Bmim]HSO4) in aqueous solution from common cellulosic sources. Two successive Taguchi experimental plans were performed to evaluate the impact of selected reaction parameters (T, t, H2O:IL ratio) and their interactions on the CNCs' yield from bleached softwood kraft pulp (SWP), bleached hardwood kraft pulp (HWP) and microcrystalline cellulose (MCC). With these experimental plans, the molar yield for extraction of nanocrystals was optimized to near theoretical levels, reaching 57.

Substitution pattern elucidation of hydroxypropyl Pinus pinaster (Ait.) bark polyflavonoid derivatives by ESI(-)-MS/MS.

The structure of condensed tannins (CTs) from Pinus pinaster bark extract and their hydroxypropylated derivatives with four degrees of substitution (DS 1, 2, 3 and 4) has been characterized for the first time using negative-ion mode electrospray ionization tandem mass spectrometry (ESI(-)-MS/MS). The results showed that P. pinaster bark CTs possess structural homogeneity in terms of monomeric units (C(15), catechin).

Rheological properties and tunable thermoplasticity of phenolic rich fraction of pyrolysis bio-oil.

In this work we report on the preparation, characterization, and properties of a thermally treated lignin-derived, phenolic-rich fraction (PRF) of wood pyrolysis bio-oil obtained by ethyl acetate extraction. The PRF was characterized for viscoelastic and rheological behavior using dynamic mechanical analysis (DMA) and cone and plate rheology. A unique thermoplastic behavior was evidenced.

Cross-linked chitosan/chitin crystal nanocomposites with improved permeation selectivity and pH stability.

This study is aimed at developing and characterizing cross-linked bionanocomposites for membrane applications using chitosan as the matrix, chitin nanocrystals as the functional phase, and gluteraldehyde as the cross-linker. The nanocomposites' chemistry and morphology were examined by estimation of gel content, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and atomic force microscopy (AFM), whereby the occurrence of cross-linking and nanoscale dispersion of chitin in the matrix was confirmed. Besides, cross-linking and chitin whiskers content were both found to impact the water uptake mechanism.

Carbon-13 cross-polarization magic-angle-spinning nuclear magnetic resonance investigation of the interactions between maleic anhydride grafted polypropylene and wood polymers.

The chemical interactions between maleic anhydride grafted polypropylene (MAPP) and wood were studied with solid-state carbon-13 cross-polarization magic-angle-spinning nuclear magnetic resonance ((13)C CPMAS NMR) spectroscopy. MAPP was synthesized with 100% (13)C enrichment at the C(1) and C(4) carbons to allow detection of the [1,4-(13)C(2)]MAPP functional groups and was melt blended with cellulose, lignin, and maple wood. In the cellulose/MAPP blend, changes in (13)C CPMAS NMR corrected signal intensities for the anhydride and dicarboxylic maleic acid functionalities suggested that esterification may have occurred predominantly from the more numerous diacid carbons.

Bioengineering bacterial cellulose/poly(ethylene oxide) nanocomposites.

By adding poly(ethylene oxide) (PEO) to the growth medium of Acetobacter xylinum, finely dispersed bacterial cellulose (BC)/PEO nanocomposites were produced in a wide range of compositions and morphologies. As the BC/PEO w/w ratio increased from 15:85 to 59:41, the cellulose nanofibers aggregated in larger bundles, indicating that PEO mixed with the cellulose on the nanometer scale [corrected]. Fourier transform infrared spectroscopy suggested intermolecular hydrogen bonding and also preferred crystallization into cellulose Ibeta in the BC/PEO nanocomposites.

Reaction tissue formation and stem tensile modulus properties in wild-type and p-coumarate-3-hydroxylase downregulated lines of alfalfa, Medicago sativa (Fabaceae).

To our knowledge, xylary reaction tissue has never been reported in a forage crop species. Here we report the discovery of reaction tissue in a transgenic line of Medicago sativa (pC3H, for the gene for p-coumarate-3-hydroxylase) with reduced lignin content and in the wild-type (WT) line. Based on microscopy and biomechanical testing of internodal alfalfa branch sections, the transgenic (pC3H-I) line, relative to the WT (1) apparently formed more reaction tissue containing gelatinous fibers with adjacent thick-walled fibers (presumed to be "intermediate" tissue) more rapidly, (2) had more xylem tissue, and (3) had comparable tensile dynamic modulus properties.