Highly regioselective surface acetylation of cellulose and shaped cellulose constructs in the gas-phase

Publisher Copyright: © 2022 The Royal Society of ChemistryGas-phase acylation is an attractive and sustainable method for modifying the surface properties of cellulosics. However, little is known concerning the regioselectivity of the chemistry, i.e., which cellulose hydroxyls are preferentially acylated and if acylation can be restricted to the surface, preserving crystallinities/morphologies. Consequently, we reexplore simple gas-phase acetylation of modern-day cellulosic building blocks - cellulose nanocrystals, pulps, dry-jet wet spun (regenerated cellulose) fibres and a nanocellulose-based aerogel. Using advanced analytics, we show that the gas-phase acetylation is highly regioselective for the C6-OH, a finding also supported by DFT-based transition-state modelling on a crystalloid surface. This contrasts with acid- and base-catalysed liquid-phase acetylation methods, highlighting that gas-phase chemistry is much more controllable, yet with similar kinetics, to the uncatalyzed liquid-phase reactions. Furthermore, this method preserves both the native (or regenerated) crystalline structure of the cellulose and the supramolecular morphology of even delicate cellulosic constructs (nanocellulose aerogel exhibiting chiral cholesteric liquid crystalline phases). Due to the soft nature of this chemistry and an ability to finely control the kinetics, yielding highly regioselective low degree of substitution products, we are convinced this method will facilitate the rapid adoption of precisely tailored and biodegradable cellulosic materials.Peer reviewe

Surface modification of cellulose nanocrystals

Cellulose nanocrystal surface modification is an expanding area in cellulose research and this thesis aims to add knowledge to this growing field. Two esterification techniques new to cellulose nanocrystal research were applied successfully to the formation of esters of (methylthio)acetic add, two pyridinum substituted benzoic acids and rnethacrylic acid. The efficacy of the two methods was compared with each other and with those used in the literature. Two click chemistry reactions were also applied to cellulose nanocrystals. Azidation of chlorinated cellulose nanocrystals allowed application of copper(I) catalysed azidealkyne cydoaddition to the grafting of two irnidazoliurn salts and ferrocene to cellulose nanocrystals. Attachment of a disulfide to cellulose nanocrystais lead to a one-pot disulfide reduction and thiol Michael addition to graft cellulose nanocrystals with pentabromobenzyl acrylate. These different surface modification strategies were used to prepare a variety of surface active nanopartides for further application. Cationic cellulose nanocrystals were produced with higher surface charge density than previously reported in the literature. The cationic nature of the nanocrystals was probed using an anionic dye adsorption methodology. The variation in anion affinity for imidazolium grafted cellulose nanocrystals was determined using a batch mixing methodology with ion chromatography. Cellulose (methylthio)acetate nanocrystals were tested as a potential supported sulfur ylid in the rhodiurn(II) acetate and sulfide co-catalysed conversion of aldehydes to epoxides. This proved unsuccessful with by-products suggesting fa ilure to form supported ylids. Finally, cellulose nanocrystals were modified with a multidentate amine ligand using a diisocyanate and the resulting nanocrystals used to bind palladiurn(II) acetate. These nanocrystals were tested in Sonogashlra reactions for recydability of the palladium catalyst. Significant leaching of the palladium catalyst occurred without the use of a copper co-catalyst and the exact nature of the palladium species present on the surface of the nanocrystals remains unknownEThOS - Electronic Theses Online ServiceGBUnited Kingdo

Imidazolium grafted cellulose nanocrystals for ion exchange applications

An imidazolium salt was grafted to cellulose nanocrystals (also called nanowhiskers) using copper(I) catalysed azide-alkyne cycloaddition and the bromide anion was successfully exchanged for bistriflimide and an anionic dye, providing the opportunity to synthesize a wide variety of ion exchange systems or catalysts using cellulose nanocrystals as a support medium.status: publishe

Controlled chlorination of polyamide reverse osmosis membranes at real scale for enhanced desalination performance

International audienceState-of-the-art desalination and water purification processes use reverse osmosis and nanofiltration membranes. Their thin polyamide (PA) top-layers ensure concurrent high water permeances and salt rejections, but are also intrinsically sensitive to chlorine, originating from disinfectant added upstream. The chlorine resistance of PA-based membranes has been thoroughly studied at lab-scale, as opposed to industrial-scale membrane modules, where fundamental studies are lacking. Therefore, to better understand chlorine-induced changes in membrane performance and physicochemical properties at industrial scale, chlorination of commercial 8” elements was conducted at different pH (4-7-10) in pressurized modules with low chlorine concentrations (0, 1, 20, 50 ppm NaOCl) during 2.5 h. After 50 ppm acidic chlorination, water permeability decreased (−40%) but salt rejection increased significantly (+0.4%, i.e., salt passage decreased with −78.8%). Boron (+27%) and isopropanol (+8%) rejection also increased. Chlorination with 20 ppm NaOCl at pH 7 and with 50 ppm NaOCl at pH 10 caused boron rejection to drop with −17% and −33%, respectively, but had negligible influence on isopropanol rejection. However, neutral and alkaline chlorination drastically improved water permeability with +40% and salt rejection with +0.6% (i.e., salt passage decreased with −66.9%), approaching and in some cases even slightly exceeding the salt/water permselectivity limit. It can thus be concluded that, under controlled conditions, chlorination can boost the performance of membrane modules. Significant changes in the membrane physicochemical properties were observed at pH 4. At pH 7 and pH 10, a low chlorine-uptake in the PA network was observed, although no significant PA deterioration was observed with XPS and ATR-FTIR. This study is the first to fundamentally investigate chlorination of PA-based real-scale membrane modules as a function of feed pH. Furthermore, it provides a promising strategy to boost membrane performance at real scale and highlights the importance of chlorination conditions

Controlled chlorination of polyamide reverse osmosis membranes at real scale for enhanced desalination performance

status: publishe

Highly charged cellulose-based nanocrystals as flocculants for harvesting Chlorella vulgaris

This study presents a novel flocculant for harvesting Chlorella vulgaris as model species for freshwater microalgae based on cellulose nanocrystals (CNCs), thus synthesized from a renewable and biodegradable resource. Cationic pyridinium groups were grafted onto CNCs by two separate one-pot simultaneous esterification and nucleophilic substitution reactions. Both types of modified CNCs were positively charged in the pH range 4-11. Both reactions yielded CNCs with a high degree of substitution (up to 0.38). A maximum flocculation efficiency of 100% was achieved at a dosage of 0.1 g g(-1) biomass. In contrast to conventional polymer flocculants, cationic CNCs were relatively insensitive to inhibition of flocculation by algal organic matter. The present results highlight the potential of these new type of nanocellulose-based flocculants for microalgae harvesting.publisher: Elsevier articletitle: Highly charged cellulose-based nanocrystals as flocculants for harvesting Chlorella vulgaris journaltitle: Bioresource Technology articlelink: http://dx.doi.org/10.1016/j.biortech.2015.07.039 content_type: article copyright: Copyright © 2015 Elsevier Ltd. All rights reserved.status: publishe

Patience is a virtue: self-assembly and physico-chemical properties of cellulose nanocrystal allomorphs

Cellulose nanocrystals (CNCs) are bio-based rod-like nanoparticles with a quickly expanding market. Despite the fact that a variety of production routes and starting cellulose sources are employed, all industrially produced CNCs consist of cellulose I (CNC-I), the native crystalline allomorph of cellulose. Here a comparative study of the physico-chemical properties and liquid crystalline behavior of CNCs produced from cellulose II (CNC-II) and typical CNC-I is reported. CNC-I and CNC-II are isolated by sulfuric acid hydrolysis of cotton and mercerized cotton, respectively. The two allomorphs display similar surface charge densities and ¿-potentials and both have a right-handed twist, but CNC-II have a slightly smaller average length and aspect ratio, and are less hygroscopic. Interestingly, the self-assembly behavior of CNC-I and CNC-II in water is different. Whilst CNC-I forms a chiral nematic phase, CNC-II initially phase separates into an upper isotropic and a lower nematic liquid crystalline phase, before a slow reorganization into a large-pitch chiral nematic texture occurs. This is potentially caused by a combination of factors, including the inferred faster rotational diffusion of CNC-II and the different crystal structures of CNC-I and CNC-II, which are responsible for the presence and absence of a giant dipole moment, respectively.Peer ReviewedPostprint (published version

Organocatalyzed ring opening polymerization of lactide from the surface of cellulose nanofibrils

International audienceThe surface initiated ring opening polymerization (SI-ROP) of cellulose nanofibers (CNF) with rac-Lactide under mild conditions using N,N-dimethyl aminopyridine (DMAP) was investigated. The influence of catalyst amount, monomer-to-initiator (cellulose surface –OH groups) ratio, temperature, and cellulose preconditioning (lyophilization vs solvent exchange) were studied to determine the best SI-ROP conditions, and to understand the effect of the parameters on grafting efficiency. The fibers modified after lyophilization had a PLA content comparable to those obtained with traditional metal catalysts (e.g. tin-(II)ethylhexanoate). Starting from a stable dispersion of CNF in dichloromethane obtained through solvent-exchange showed better results at low catalyst amounts. Furthermore, DMAP was readily removed from the products whereas metal catalysts can be hard to remove from the final material, potentially shortening the material lifespan and making it unfit for some applications. Therefore, the use of an easily removable and more efficient organocatalyst can be considered a good alternative to metal catalysts

Organocatalyzed ring opening polymerization of lactide from the surface of cellulose nanofibrils

The surface initiated ring opening polymerization (SI-ROP) of cellulose nanofibers (CNF) with rac-Lactide under mild conditions using N,N-dimethyl aminopyridine (DMAP) was investigated. The influence of catalyst amount, monomer-to-initiator (cellulose surface -OH groups) ratio, temperature, and cellulose preconditioning (lyophilization vs solvent exchange) were studied to determine the best SI-ROP conditions, and to understand the effect of the parameters on grafting efficiency. The fibers modified after lyophilization had a PLA content comparable to those obtained with traditional metal catalysts (e.g. tin-(II)ethylhexanoate). Starting from a stable dispersion of CNF in dichloromethane obtained through solvent-exchange showed better results at low catalyst amounts. Furthermore, DMAP was readily removed from the products whereas metal catalysts can be hard to remove from the final material, potentially shortening the material lifespan and making it unfit for some applications. Therefore, the use of an easily removable and more efficient organocatalyst can be considered a good alternative to metal catalysts.status: publishe

Patience is a virtue: self-assembly and physico-chemical properties of cellulose nanocrystal allomorphs

Cellulose nanocrystals (CNCs) are bio-based rod-like nanoparticles with a quickly expanding market. Despite the fact that a variety of production routes and starting cellulose sources are employed, all industrially produced CNCs consist of cellulose I (CNC-I), the native crystalline allomorph of cellulose. Here a comparative study of the physico-chemical properties and liquid crystalline behavior of CNCs produced from cellulose II (CNC-II) and typical CNC-I is reported. CNC-I and CNC-II are isolated by sulfuric acid hydrolysis of cotton and mercerized cotton, respectively. The two allomorphs display similar surface charge densities and ζ-potentials and both have a right-handed twist, but CNC-II have a slightly smaller average length and aspect ratio, and are less hygroscopic. Interestingly, the self-assembly behavior of CNC-I and CNC-II in water is different. Whilst CNC-I forms a chiral nematic phase, CNC-II initially phase separates into an upper isotropic and a lower nematic liquid crystalline phase, before a slow reorganization into a large-pitch chiral nematic texture occurs. This is potentially caused by a combination of factors, including the inferred faster rotational diffusion of CNC-II and the different crystal structures of CNC-I and CNC-II, which are responsible for the presence and absence of a giant dipole moment, respectively.status: publishe