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Cellulose (CNF) and chitin (ChNF) nanofibers are known to form materials that are both tough and strong. In this study, we hypothesize that the inertness of networks produced from CNF and ChNF makes them ideal templates for heterogeneous reactions and in situ formation of nanoarchitectures. We expand nanoparticle templating on polysaccharide colloids by introducing a new and facile process that leads to the growth of organic nanoparticles on CNF and ChNF in aqueous media. The process, based on solvent shifting supported on solid interfaces, is demonstrated by direct observation of lignin nanoparticles that are further used for their photocatalytic activity. Importantly, the dynamics of nanoparticle nucleation and growth is correlated with the surface chemistry of the templating nanopolysaccharides. Electrostatic repulsion between the deprotonated lignin molecules and the slightly negative CNF support led to limited adsorption and was effective in producing free (nonbound) lignin nanoparticles (28 ± 7 nm) via precipitation. In contrast, the stronger interfacial interactions between the positively charged ChNF and lignin molecules facilitated instantaneous and extensive lignin adsorption, followed by nucleation and growth into relatively larger nanoparticles (46 ± 17 nm). The latter were homogeneously distributed and strongly coupled to the ChNF support. Overall, we introduce lignin nanoparticle nucleation and growth on renewable nanopolysaccharides, offering an effective route toward in situ synthesis of highly functional fibrils and related cohesive films that offer a great potential in packaging and other applications.
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Nanofibras , Nanopartículas , Celulose , Quitina , LigninaRESUMO
The use of capillary systems in space and biotechnology applications requires the regulation of the capillary flow velocity. It has been observed that constricted sections act as flow resistors. In this work, we also show that enlarged sections temporarily reduce the velocity of the flow. In this work, the theory of the dynamics of capillary flows passing through a constricted or an enlarged channel section is presented. It is demonstrated that the physics of a capillary flow in a channel with a constriction or an enlargement is different and that a constriction acts as a global flow resistor and an enlargement as a local flow resistor. The theoretical results are checked against experimental approaches.
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An environmentally friendly and simple method, named SolReact, has been developed for a solvent-free esterification of cellulose nanocrystals (CNC) surface by using two nontoxic carboxylic acids (CA), phenylacetic acid and hydrocinnamic acid. In this process, the carboxylic acids do not only act as grafting agent, but also as solvent media above their melting point. Key is the in situ solvent exchange by water evaporation driving the esterification reaction without drying the CNC. Atomic force microscopy and X-ray diffraction analyses showed no significant change in the CNC dimensions and crystallinity index after this green process. The presence of the grafted carboxylic was characterized by analysis of the "bulk" CNC with elemental analysis, infrared spectroscopy, and (13)C NMR. The ability to tune the surface properties of grafted nanocrystals (CNC-g-CA) was evaluated by X-ray photoelectron spectroscopy analysis. The hydrophobicity behavior of the functionalized CNC was studied through the water contact-angle measurements and vapor adsorption. The functionalization of these bionanoparticles may offer applications in composite manufacturing, where these nanoparticles have limited dispersibility in hydrophobic polymer matrices and as nanoadsorbers due to the presence of phenolic groups attached on the surface.
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Ácidos Carboxílicos/química , Celulose/química , Nanopartículas/química , Esterificação , Química Verde , Interações Hidrofóbicas e Hidrofílicas , Espectroscopia de Ressonância Magnética , Microscopia de Força Atômica , Espectroscopia Fotoeletrônica , Polímeros/química , Solventes/química , Espectrofotometria Infravermelho , Propriedades de Superfície , Água/química , Difração de Raios XRESUMO
Cellulose nanofibrils were efficiently produced from eucalyptus fibers using a combined NaOH and enzymatic treatment followed by a pilot scale grinding process. The structural changes of fibers were assessed after NaOH treatments at 5, 10 and 15 wt% concentrations. A progressive shift from a cellulose I to a cellulose II crystalline structure was observed with X-ray diffraction (XRD) and nuclear magnetic resonance (NMR). The further enzymatic hydrolysis was improved for the NaOH treated samples. The increase of crystallinity indices due to enzymatic hydrolysis was of + 4.7 %, + 3.5 %, and +10.3 % for samples treated with NaOH 5, 10 and 15 wt% respectively, and DP values were drastically reduced to 340, 190 and 166 respectively. A morphological analysis underlined an optimum with the combination of NaOH 10 wt% and enzymatic hydrolysis. This treatment followed by the grinding process resulted in CNF with a rigid structure, with diameters ranging from 10 to 20 nm and lengths between 150 and 350 nm. A multi-scale analysis enabled to study the impact of this combined treatment on CNF properties and energy consumption. A decrease in mechanical properties of nanopapers was observed for the combined treatment and NaOH treatment alone compared to enzymatic hydrolysis alone, with Young's modulus of 8.94, 4.84 and 11.21 GPa respectively. However, optical properties were improved, with transmittance values of 42.2, 15.4 and 7.1 % respectively. This new pretreatment can therefore lead to CNF with tunable properties depending on the application, with possible industrialization thanks to the reduction of energy needs.
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Celulose/química , Eucalyptus/química , Nanofibras/química , Hidróxido de Sódio/química , Biomassa , Cristalização , Módulo de Elasticidade , Hidrólise , Teste de Materiais/métodos , Nanofibras/ultraestruturaRESUMO
The aim of this work was to study the cellulose fibers deconstruction by twin-screw extrusion with in situ enzymatic hydrolysis via bioextrusion, for cellulose nanofibrils (CNF) production. Cellulose pulp was extruded with an optimized screw profile, with or without (reference) the addition of an enzymatic solution. An increase of crystallinity index from 67.0% to 73.7% and decrease of DP from 1003 to 419 were observed with bioextrusion. Direct activity measurements of the enzyme confirmed its activity during the process (sugar content increasing from 0.07 ± 0.004 to 2.38 ± 0.003 mg/mL) and after the process (specific activities around 0.20 CMCU/mL). Enzymes were not deactivated during bioextrusion and could be recycled. CNF properties were higher with bioextrusion compared to reference (respective quality indices of 55.5 ± 2.7 and 39.8 ± 2.8), with a lower energy consumption. This proof of concept could be optimized for the industrial production of highly concentrated CNF.
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Carboidratos , Celulose , Hidrólise , Reciclagem , AçúcaresRESUMO
Nowadays, drug encapsulation and drug release from cellulose nanofibrils systems are intense research topics, and commercial grades of cellulose nanomaterials are currently available. In this work we present an ester-containing prodrug of metronidazole that is covalently bound to cellulose nanofibrils in aqueous suspension through a two-step immobilization procedure involving green chemistry principles. The presence of the drug is confirmed by several characterization tools and methods such as Raman spectroscopy, elemental analysis, Dynamic Nuclear Polarization enhanced NMR. This technique allows enhancing the sensitivity of NMR by several orders of magnitude. It has been used to study cellulose nanofibrils substrates and it appears as the ultimate tool to confirm the covalent nature of the binding through thiol-yne click chemistry. Moreover, the ester function of the immobilized prodrug can be cleaved by specific enzyme activity thus allowing controlled drug release.
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Celulose/química , Química Click/métodos , Metronidazol/química , Nanofibras/química , Pró-Fármacos/química , Antibacterianos/química , Óxidos N-Cíclicos/química , Preparações de Ação Retardada/química , Humanos , Espectroscopia de Ressonância Magnética/métodos , Oxirredução , Análise Espectral Raman/métodos , Compostos de Sulfidrila/química , Água/químicaRESUMO
Chemical modifications of cellulose fibers as pretreatment for cellulose nanofibrils (CNF) production have been investigated to improve the production process and the quality of obtained cellulosic nanomaterial. In this study, phosphorylation of cellulose fibers was done in anticipation of a future nanofibrillation. Different phosphate salts, namely NH4H2PO4, (NH4)2HPO4, Na2HPO4, NaH2PO4 and LiH2PO4 with different constants of solubility (Ks) were used to increase the efficiency of the modification. Phosphorylated cellulose pulps were analyzed using elemental analysis, solid-state 13C and 31P NMR, or conductimetric titration method. No effect of Ks was observed whereas a counterion effect was pointed out. The study also reported the effect of pH, cellulose consistency, temperature and urea content in phosphorylation efficiency. Finally, chemical functionalization and penetration of phosphorylation reagents in the cellulose fibers were evaluated using XPS, SEM-EDX, ToF-SIMS and solid-state NMR.
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Cellulose nanocrystals (CNCs) are used to design nanocomposites because of their high aspect ratio and their outstanding mechanical and barrier properties. However, the low compatibility of hydrophilic CNCs with hydrophobic polymers remains a barrier to their use in the nanocomposite field. To improve this compatibility, poly(glycidyl methacrylate) (PGMA) was grafted from CNCs containing α-bromoisobutyryl moieties via surface-initiated atom transfer radical polymerization. The novelty of this research is the use of a reactive epoxy-containing monomer that can serve as a new platform for further modifications or crosslinking. Polymer-grafted CNC-PGMA-Br prepared at different polymerization times were characterized by XRD, DLS, FTIR, XPS and elemental analysis. Approximately 40 % of the polymer at the surface of the CNCs was quantified after only 1â¯h of polymerization. Finally, nanocomposites prepared with 10â¯wt% CNC-PGMA-Br as nanofillers in a poly(lactic acid) (PLA) matrix exhibited an improvement in their compatibilization based on SEM observation.
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Celulose/química , Compostos de Epóxi/síntese química , Metacrilatos/síntese química , Nanocompostos/química , Nanopartículas/química , Poliésteres/química , Compostos de Epóxi/química , Metacrilatos/química , Tamanho da Partícula , Polimerização , Propriedades de SuperfícieRESUMO
Cellulose nanofibrils (CNF) are renewable bio-based materials with high specific area, which makes them ideal candidates for multiple emerging applications including for instance on-demand drug release. However, in-depth chemical and structural characterization of the CNF surface chemistry is still an open challenge, especially for low weight percentage of functionalization. This currently prevents the development of efficient, cost-effective and reproducible green synthetic routes and thus the widespread development of targeted and responsive drug-delivery CNF carriers. We show in this work how we use dynamic nuclear polarization (DNP) to overcome the sensitivity limitation of conventional solid-state NMR and gain insight into the surface chemistry of drug-functionalized TEMPO-oxidized cellulose nanofibrils. The DNP enhanced-NMR data can report unambiguously on the presence of trace amounts of TEMPO moieties and depolymerized cellulosic units in the starting material, as well as coupling agents on the CNFs surface (used in the heterogeneous reaction). This enables a precise estimation of the drug loading while differentiating adsorption from covalent bonding (â¼1 wt% in our case) as opposed to other analytical techniques such as elemental analysis and conductometric titration that can neither detect the presence of coupling agents, nor differentiate unambiguously between adsorption and grafting. The approach, which does not rely on the use of 13C/15N enriched compounds, will be key to further develop efficient surface chemistry routes and has direct implication for the development of drug delivery applications both in terms of safety and dosage.
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Process simulation is a useful tool that has been widely used to analyze, design and optimize energy balances in chemical technologies including those related to biomass processing, biorefinery processes and chemical engineering. The presented data set serves as basis for the simulation of chitin purification, nanofibers and nanocrystals production processes, considering laboratory experimental procedures described in previous experimental articles.
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Chitin nanocrystals (ChNCs) and chitin nanofibers (ChNFs) are nanomaterials with great innovative potential for sustainable applications in academic and industrial fields. The research related to their isolation and production, characterization, and utilization is still new. The aim of this study is to investigate the effects of the production process on the morphology and properties of ChNFs and ChNCs produced from the same source of chitin. ChNCs were prepared by acid hydrolysis of commercial shrimp shell α-chitin, and ChNFs were prepared by mechanical defibrillation using closed loop supermass colloidal grinding. Differences in their shape, size, and crystallinity were observed. ChNFs were observed to have higher aspect ratio, higher viscosity, and better thermal stability than ChNCs. Although the ChNC casting film had a higher degree of transparency, it had lower mechanical properties than ChNF film. In addition, the capacities of each nanomaterial for producing Pickering emulsions were comparatively investigated. ChNFs showed better oil-in-water emulsion stabilization ability than ChNCs at the same concentrations. In vitro cytotoxicity assays using two epithelial-like cell lines and two fibroblast-like cell lines demonstrated that both nanomaterials were non-toxic. Finally, we evaluated the economics of production using process engineering simulation to assess the energy and chemical consumption for each process of production of these nanomaterials.
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Nanocomposites are an opportunity to increase the performance of polymer membranes by fine-tuning their morphology. In particular, the understanding of the contribution of the polymer matrix/nanofiller interface to the overall transport properties is key to design membranes with tailored selective and adsorptive properties. In that aim, cellulose nanocrystals (CNC)/polylactide (PLA) nanocomposites were fabricated with chemically designed interfaces, which were ensuring the compatibility between the constituents and impacting the mass transport mechanism. A detailed analysis of the mass transport behaviour of different permeants in CNC/PLA nanocomposites was carried out as a function of their chemical affinity to grafted CNC surfaces. Penetrants (O2 and cyclohexane), which were found to slightly interact with the constituents of the nanocomposites, provided information on the small tortuosity effect of CNC on diffusive mass transport. The mass transport of water (highly interacting with CNC) and anisole (interacting only with designed CNC surfaces) exhibited non-Fickian, Case II behaviour. The water vapour caused significant swelling of the CNC, which created a preferential pathway for mass transport. CNC surface grafting could attenuate this phenomenon and decrease the water transport rate. Anisole, an aromatic organic vapour, became reversibly trapped at the specifically designed CNC/PLA interface, but without any swelling or creation of an accelerated pathway. This caused the decrease of the overall mass transport rate. The latter finding could open a way to the creation of materials with specifically designed barrier properties by designing nanocomposites interfaces with specific interactions towards permeants.
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Surface functionalization of cellulose nanocrystals (CNCs) aims to improve their properties. The main objective of this study was the esterification of the surface of CNCs using nontoxic resin acids, rosin. The structural and morphological modifications of CNC nanorods were characterized by (13)C NMR and Fourier transform infrared spectroscopy, atomic force microscopy, and X-ray diffraction analyses. The properties of functionalized CNCs were evaluated by thermogravimetric analysis and contact-angle measurements. The results indicate that the esterification proceeded from the surface of the CNC. The antimicrobial activities of the modified and neat CNC were investigated; the rosin-grafted CNC exhibited a strong antibacterial activity against Gram-negative bacteria and a modest antibacterial activity against Gram-positive bacteria.
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Anti-Infecciosos/química , Celulose/química , Nanopartículas/química , Resinas Vegetais/químicaRESUMO
One property of sulfated cellulose nanocrystals (CNCs) is their ability to self-assemble from a concentrated suspension under specific drying conditions into an iridescent film. Such colored films are very brittle, which makes them difficult to handle or integrate within an industrial process. The goal of this study is (i) to produce flexible films using neutral poly(ethylene glycol) (PEG) and (ii) to modulate their coloration using an anionic polyacrylate (PAAS). The first part is dedicated to studying the physicochemical interactions of the two polymers with CNCs using techniques such as zeta potential measurements, dynamic light scattering (DLS), quartz crystal microbalance (QCM), and atomic force microscopy (AFM). Iridescent solid films were then produced and characterized using scanning electron microscopy (SEM) and UV-visible spectroscopy. The mechanical and thermal properties of films incorporating CNC were measured to evaluate improvements in flexibility. The addition of 10 wt % of PEG makes these films much more flexible (with a doubling of the elongation), with the coloration being preserved and the temperature of degradation increasing by almost 35 °C. Up to 160 µmol/gCNC PAAS can be added to tune the coloration of the CNC films by producing a more narrow, stronger coloration in the visible spectrum (higher absorption) with a well-pronounced fingerprint texture.
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Contact active surfaces are an innovative tool for developing antibacterial products. Here, the microfibrillated cellulose (MFC) surface was modified with the ß-lactam antibiotic benzyl penicillin in aqueous medium to prepare antimicrobial films. Penicillin was grafted on the MFC surface using a suspension of these nanofilaments or directly on films. Films prepared from the penicillin-modified MFC were characterized by Fourier transform infrared spectroscopy, contact angle measurements, elemental analysis, and X-ray photoelectron spectroscopy and tested for antibacterial activity against the Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli. Penicillin-grafted MFC films exhibited successful killing effect on Gram-positive bacteria with 3.5-log reduction whereas bacteriostatic efficiency was found in penicillin-grafted MFC suspension. The zone of inhibition test and leaching dynamic assay demonstrated that penicillin was not diffused into the surrounding media, thus proving that the films were indeed contact active. Thus, penicillin can be chemically bound to the modified substrate surface to produce promising nonleaching antimicrobial systems.
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Anti-Infecciosos/química , Celulose/química , Anti-Infecciosos/farmacologia , Testes de Sensibilidade a Antimicrobianos por Disco-Difusão , Escherichia coli/efeitos dos fármacos , Penicilinas/química , Penicilinas/farmacologia , Espectroscopia Fotoeletrônica , Espectroscopia de Infravermelho com Transformada de Fourier , Staphylococcus aureus/efeitos dos fármacos , Propriedades de Superfície , Água/químicaRESUMO
A simple method to produce biobased iridescent pigments from cellulose nanocrystal (CNC) films is reported. The process consists of forming nanostructured films from a CNC liquid-crystalline suspension and an appropriate dry grinding. The features of the iridescent pigments are described; they have a flake-like morphology with a thickness of 25 µm. However, because of the presence of sulfate groups, thermal degradation and high redispersion in water occur, which affect the iridescent property of these biobased pigments. To overcome such limitations, two post-treatments are proposed. The sulfate ester groups are removed from the iridescent pigments with vacuum overdrying. The mass loss of iridescent pigment in water is reduced with an increase of the ionic strength in the aqueous medium by NaCl addition. These post-treatments have proven to be efficient and engineered pigments based on CNC films can be used to add anticounterfeiting features to packaging manufactured by classical paper techniques or extrusion.