Naceur Belgacem

Flexibility and Color Monitoring of Cellulose Nanocrystal Iridescent Solid Films Using Anionic or Neutral Polymers

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.

Green process for chemical functionalization of nanocellulose with carboxylic acids.

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.

Surface grafting of cellulose nanocrystals with natural antimicrobial rosin mixture using a green process.

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.

Substitution of nanoclay in high gas barrier films of cellulose nanofibrils with cellulose nanocrystals and thermal treatment

The aim of this study is to design a nanocellulose based barrier film. For this purpose, cellulose nanofibrils (CNFs) are used as a matrix to create an entangled nanoporous network that is filled with two different nanofillers: nanoclay (reference), i.e. the mineral montmorillonite (MMT) and the bio-based TEMPO-oxidized cellulose nanocrystal (CNC-T), to produce different types of nanocelluloses and their main physical and chemical features were assessed. As expected, films based on neat CNFs exhibit good mechanical performance and excellent barrier properties at low moisture content. The introduction of 32.5xa0wt% of either nanofiller results in a significant improvement of barrier properties at high moisture content. Finally, thermal treatment of a dried CNF/CNC-T film results in a decrease of the oxygen permeability even at high moisture content (>70xa0%). This is mainly attributed to the hornification of nanocellulose. A key result of this study is that the oxygen permeability of an all-nanocellulose film in 85xa0% relative humidity (RH), is similar to CNF film with mineral nanoclay (MMT), i.e. 2.1 instead of 1.7xa0cm3xa0µmxa0m−2xa0day−1xa0kPa−1, respectively.

Contact Antimicrobial Surface Obtained by Chemical Grafting of Microfibrillated Cellulose in Aqueous Solution Limiting Antibiotic Release

Contact active surfaces are an innovative tool for developing antibacterial products. Here, the microfibrillated cellulose (MFC) surface was modified with the β-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.

Effect of different carboxylic acids in cyclodextrin functionalization of cellulose nanocrystals for prolonged release of carvacrol.

Current investigations deal with new surface functionalization strategy of nanocrystalline cellulose-based substrates to impart active molecule release properties. In this study, cellulose nanocrystals (CNC) were surface-functionalized with β-cyclodextrin (β-CD) using succinic acid (SA) and fumaric acid (FA) as bridging agents. The main objective of this surface modification performed only in aqueous media was to obtain new active materials able to release antibacterial molecules over a prolonged period of time. The reactions were conducted by immersing the CNC film into a solution composed of β-CD, SA and FA, leading to CNC grafting. The materials were characterized by infrared spectroscopy (FT-IR), Quartz crystal microbalance-dissipation (QCM-D), AFM and phenolphthalein (PhP) was used to determine the efficiency of CNC grafting with β-CD. The results indicated that β-CD was successfully attached to the CNC backbone through the formation of ester bonds. Furthermore, carvacrol was entrapped by the attached β-CD and a prolonged release was confirmed. In particular, CNC grafted to β-CD in the presence of FA was selected as the best solution. The antibacterial activity and the controlled release were studied for this sample. Considerably longer bacterial activity against B. subtilis was observed for CNC grafted to β-CD compared to CNC and CNC-FA, confirming the promising impact of the present strategy.

Capillary Flow Resistors: Local and Global Resistors

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.

Cellulose nanocrystal surface functionalization for the controlled sorption of water and organic vapours

The surface grafting of cellulose nanocrystals (CNC) is a valuable tool to increase opportunities for their application. This work had several goals designed to improve CNC: reduction of hornification, increased re-dispersibility after CNC drying, and tuning of the surface graft to enhance the adsorption of particular molecules. To achieve this, the CNC surfaces were modified chemically with aromatic surface grafts using widely employed methods: the creation of urethane linkages, silylation and esterification. Even a low degree of grafting sufficed to increase water contact angles to as much as 96°. The analysis of water sorption isotherms showed that at high water activities, capillary condensation could be suppressed and hysteresis was decreased. This indicates that hornification was significantly suppressed. However, although the contact angles increased, the water sorption isotherms were changed only slightly because of reduced hysteresis. The grafts were not able to shield the surface from water vapour sorption. A comparison of the sorption isotherms of anisole and cyclohexane, sorbates with a similar surface area, showed that the sorption of anisole was three times higher than that of cyclohexane. The specific sorption of aromatic molecules was achieved and the most efficient methodology was the esterification of CNC with carboxylic acids containing a flexible linker between the aromatic moiety and ester bond.

Designed cellulose nanocrystal surface properties for improving barrier properties in polylactide nanocomposites

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.

Controlled release of carvacrol and curcumin: bio-based food packaging by synergism action of TEMPO-oxidized cellulose nanocrystals and cyclodextrin

AbstractnOxidized cellulose nanocrystals with sodium carboxylate groups (TOCNC-COONa) and with free carboxyl groups (TOCN-COOH) were prepared and then chemically modified with beta-cyclodextrin (βCD) and hydroxypropyl-beta-cyclodextrin (HPβCD) to prepare materials able to load and release antibacterial molecules over a prolonged period of time. The materials were characterized by infrared spectroscopy, and the CD content of modified TOCNCs determined by phenolphthalein colorimetry. The extent of grafting was also assessed by QCM-D and microscopy was used to ascertain and compare the morphology of both TOCNC-COONa/HPβCD and TOCNC-COOH/HPβCD. Then, carvacrol and curcumin were entrapped by the attached HPβCD and their prolonged release confirmed, as compared to neat material. The combined effects of HPβCD and carvacrol on the antimicrobial properties of TOCNC-COOH films were finally evaluated.