Laboratoire de génie des procédés pour la bioraffinerie, les matériaux bio-sourcés et l’impression fonctionnelle

Nanomaterials (NMs) have gained prominence in technological advancements due to their tunable physical, chemical and biological properties with enhanced performance over their bulk counterparts. NMs are categorized depending on their size, composition, shape, and origin. The ability to predict the unique properties of NMs increases the value of each classification. Due to increased growth of production of NMs and their industrial applications, issues relating to toxicity are inevitable. The aim of this review is to compare synthetic (engineered) and naturally occurring nanoparticles (NPs) and nanostructured materials (NSMs) to identify their nanoscale properties and to define the specific knowledge gaps related to the risk assessment of NPs and NSMs in the environment. The review presents an overview of the history and classifications of NMs and gives an overview of the various sources of NPs and NSMs, from natural to synthetic, and their toxic effects towards mammalian cells and tissue. Additionally, the types of toxic reactions associated with NPs and NSMs and the regulations implemented by different countries to reduce the associated risks are also discussed.

Starch is a natural, renewable, and biodegradable polymer produced by many plants as a source of stored energy. It is the second most abundant biomass material in nature. The starch structure has been under research for years, and because of its complexity, an universally accepted model is still lacking (Buleon, A.; et al. Int. J. Biol. Macromol. 1998, 23, 85-112). However, the predominant model for starch is a concentric semicrystalline multiscale structure that allows the production of new nanoelements: (i) starch nanocrystals resulting from the disruption of amorphous domains from semicrystalline granules by acid hydrolysis and (ii) starch nanoparticles produced from gelatinized starch. This paper intends to give a clear overview of starch nanoparticle preparation, characterization, properties, and applications. Recent studies have shown that they could be used as fillers to improve mechanical and barrier properties of biocomposites. Their use for industrial packaging, continuously looking for innovative solutions for efficient and sustainable systems, is being investigated. Therefore, recently, starch nanoparticles have been the focus of an exponentially increasing number of works devoted to develop biocomposites by blending starch nanoparticles with different biopolymeric matrices. To our knowledge, this topic has never been reviewed, despite several published strategies and conclusions.

A new family of materials comprised of cellulose, cellulose nanomaterials (CNMs), having properties and functionalities distinct from molecular cellulose and wood pulp, is being developed for applications that were once thought impossible for cellulosic materials. Commercialization, paralleled by research in this field, is fueled by the unique combination of characteristics, such as high on-axis stiffness, sustainability, scalability, and mechanical reinforcement of a wide variety of materials, leading to their utility across a broad spectrum of high-performance material applications. However, with this exponential growth in interest/activity, the development of measurement protocols necessary for consistent, reliable and accurate materials characterization has been outpaced. These protocols, developed in the broader research community, are critical for the advancement in understanding, process optimization, and utilization of CNMs in materials development. This review establishes detailed best practices, methods and techniques for characterizing CNM particle morphology, surface chemistry, surface charge, purity, crystallinity, rheological properties, mechanical properties, and toxicity for two distinct forms of CNMs: cellulose nanocrystals and cellulose nanofibrils.

Interest in nanofibrillated cellulose (NFC) has increased notably over recent decades. This bio-based nanomaterial has been used essentially in bionanocomposites or in paper thanks to its high mechanical reinforcement ability or barrier property respectively. Its nano-scale dimensions and its capacity to form a strong entangled nanoporous network have encouraged the emergence of new high-value applications. It is worth noting that chemical surface modification of this material can be a key factor to achieve a better compatibility with matrices. In order to increase the compatibility in different matrices or to add new functions, surface chemical modification of NFC appears to be the prior choice to conserve its intrinsic nanofibre properties. In this review, the authors have proposed for the first time an overview of all chemical grafting strategies used to date on nanofibrillated cellulose with focus on surface modification such as physical adsorption, molecular grafting or polymer grafting.

Since the last decade, interest in cellulose nanomaterials known as nanocellulose has been growing. Nanocellulose has various applications ranging from composite reinforcement to rheological modifiers. Recently, nanocellulose has been shown to have great potential in flexible printed electronics applications. The property of nanocellulose to form self-standing thermally stable films has been exploited for producing transparent and smooth substrates for printed electronics. However, other than substrates, the field of printed electronics involves the use of inks, various processing methods and the production of flexible electronic devices. This review aims at providing an overview of the use and potential of nanocellulose throughout the printed electronics field.

The interest in using cellulose fibres as reinforcing elements in composite materials based on polymeric matrices is constantly growing, mainly because of the many advantages associated with this renewable material. However, the preparation of cellulose-based composites is perturbed by the highly hydrophilic character of the fibres, which is associated with a low interfacial compatibility with hydrophobic polymeric matrices, as well as with a loss of mechanical properties after moisture uptake. In order to reduce the hydrophilic character of cellulose fibres and to improve the strength of their adhesion to the matrix, it is necessary to undertake a structural modification of their surface. Several approaches have been studied, namely (i) physical treatments such as corona, plasma, laser, vacuum ultraviolet and γ-radiation treatments; (ii) chemical grafting by direct condensation, including surface compatibilisation with hydrophobic moieties and co-polymerisation with the matrix. The copolymerisation approach called upon different strategies: (i) The use of bi-functional molecules capable of reacting with the OH groups of the cellulose surface and leaving the second functions available for further exploitation; (ii) The direct activation of the surface and the subsequent graftingfrom polymerisation; and (iii) The condensation of organometallic compounds, followed by their coupling with suitable reactive molecules or macromolecules. The characterisation of the modified surfaces involved a variety of techniques, including elemental analysis, contact angle measurements, inverse gas chromatography, X-ray photoelectron and FTIR spectroscopy, water uptake, etc. The present survey reviews the different approaches proposed in the literature and critically assesses their respective merits and drawbacks.

Abstract The viscoplastic deformation (creep) of crystalline materials under constant stress involves the motion of a large number of interacting dislocations1. Analytical methods and sophisticated ‘dislocation dynamics’ simulations have proved very effective in the study of dislocation patterning, and have led to macroscopic constitutive laws of plastic deformation2, 3, 4, 5, 6, 7, 8, 9. Yet, a statistical analysis of the dynamics of an assembly of interacting dislocations has not hitherto been performed. Here we report acoustic emission measurements on stressed ice single crystals, the results of which indicate that dislocations move in a scale-free intermittent fashion. This result is confirmed by numerical simulations of a model of interacting dislocations that successfully reproduces the main features of the experiment. We find that dislocations generate a slowly evolving configuration landscape which coexists with rapid collective rearrangements. These rearrangements involve a comparatively small fraction of the dislocations and lead to an intermittent behaviour of the net plastic response. This basic dynamical picture appears to be a generic feature in the deformation of many other materials10, 11, 12. Moreover, it should provide a framework for discussing fundamental aspects of plasticity that goes beyond standard mean-field approaches that see plastic deformation as a smooth laminar flow.

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Cellulose nanofibrils (CNFs) are produced and commonly used in the form of aqueous suspensions or gels. A number of studies have focused lately on rheological properties of CNF suspensions, which gives insight into properties of such materials and can reflect their behavior during handling. This Review summarizes the recent progress in rheological studies on CNF aqueous suspensions using rotational rheometry. Here, we discuss linear viscoelastic properties, i.e., frequency-dependent storage and loss moduli; shear flow behavior, i.e., apparent viscosity and shear stress as a function of shear rate; local flow characteristics, etc. In this Review, we point out that the rheological behavior of at least two types of CNF suspensions should be distinguished: (i) ones produced using mechanical fibrillation with or without enzymatic pretreatment (no surface chemical modification), which possess highly flocculated structure, and (ii) ones produced involving chemical modification pretreatments, e.g., carboxylation, carboxymethylation, quaternization, or sulfonation, which possess better colloidal stability and do not evidently flocculate.

BACKGROUND: An accurate estimation of the risk of life-threatening (LT) ventricular tachyarrhythmia (VTA) in patients with LMNA mutations is crucial to select candidates for implantable cardioverter-defibrillator implantation. METHODS: We included 839 adult patients with LMNA mutations, including 660 from a French nationwide registry in the development sample, and 179 from other countries, referred to 5 tertiary centers for cardiomyopathies, in the validation sample. LTVTA was defined as (1) sudden cardiac death or (2) implantable cardioverter defibrillator-treated or hemodynamically unstable VTA. The prognostic model was derived using the Fine-Gray regression model. The net reclassification was compared with current clinical practice guidelines. The results are presented as means (SD) or medians [interquartile range]. RESULTS: We included 444 patients, 40.6 (14.1) years of age, in the derivation sample and 145 patients, 38.2 (15.0) years, in the validation sample, of whom 86 (19.3%) and 34 (23.4%) experienced LTVTA over 3.6 [1.0-7.2] and 5.1 [2.0-9.3] years of follow-up, respectively. Predictors of LTVTA in the derivation sample were: male sex, nonmissense LMNA mutation, first degree and higher atrioventricular block, nonsustained ventricular tachycardia, and left ventricular ejection fraction (https://lmna-risk-vta.fr). In the derivation sample, C-index (95% CI) of the model was 0.776 (0.711-0.842), and the calibration slope 0.827. In the external validation sample, the C-index was 0.800 (0.642-0.959), and the calibration slope was 1.082 (95% CI, 0.643-1.522). A 5-year estimated risk threshold ≥7% predicted 96.2% of LTVTA and net reclassified 28.8% of patients with LTVTA in comparison with the guidelines-based approach. CONCLUSIONS: In comparison with the current standard of care, this risk prediction model for LTVTA in laminopathies significantly facilitated the choice of candidates for implantable cardioverter defibrillators. CLINICAL TRIAL REGISTRATION: URL: https://www.clinicaltrials.gov. Unique identifier: NCT03058185.

This chapter describes the chemistry and structure of cellulose fibers and the existing extraction methods for various kinds of nanocellulose (NC), such as cellulose nanofibrils (CNFs), cellulose nanocrystals (CNCs), amorphous nanocellulose (ANC), and cellulose nanoyarn (CNY). Specific conditions for extraction of NC from various natural sources are discussed in detail. The effects of the extraction methods, pretreatments, and conditions on the structure, morphology, and properties of isolated NC are described.

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.

The present work investigates the formation conditions and the latent heat of dissociation of hydrates formed from tetrahydrofuran (THF)-CO2-water mixtures. The conditions investigated are 3.8-15 wt % for THF concentration and 0.2-3.5 MPa for the CO2 partial pressure range, conditions that are adapted to the use of the corresponding hydrate slurries as secondary refrigerants. Both differential thermal analysis (DTA) and differential scanning calorimetry (DSC) methods were used for the experimental determinations. Experimental\nvalues were compared with modeling, combining the van der Waals and Platteeuw approach with the Redlich-Kwong equation of state associated to a modified Huron-Vidal (MHV2) mixing rule. At fixed temperature, adding THF to the systems results in a drastic reduction of CO2 equilibrium pressure. For instance, at 280 K, a 78.9% decrease of CO2 pressure is experimentally observed if the solution contains 3.8 wt % of THF. Furthermore, a dissociation enthalpy of (CO2 + THF) hydrates roughly two times higher that that of CO2 hydrates was calculated from measured and predicted data of hydrate formation.

Abstract Nanocomposites of cassava starch reinforced with waxy starch nanocrystals were prepared. They showed a 380% increase of the rubbery storage modulus (at 50 °C) and a 40% decrease in the water vapor permeability. X‐ray spectra show that the composite was more amorphous than the neat matrix, which was attributed to higher equilibrium water content in the composites. TGA confirmed this result and its thermal derivative suggested the formation of hydrogen bonding between glycerol and the nanocrystals. The reinforcing effect of starch nanocrystals was attributed to strong filler/matrix interactions due to the hydrogen bonding. The decrease of the permeability suggests that the nanocrystals were well dispersed, with few filler/filler interactions. magnified image

There are numerous examples where animals or plants synthesize extracellular high-performance skeletal biocomposites consisting of a matrix reinforced by fibrous biopolymers. Cellulose and chitin are classical examples of these reinforcing elements, which occur as whisker-like microfibrils that are biosynthesized and deposited in a continuous fashion. In many cases, this mode of biogenesis leads to crystalline microfibrils that are almost defect-free, with the consequence of axial physical properties approaching those of perfect crystals. Starch is another example of natural semicrystalline polymer that is produced by many plants and occurs as microscopic granules. It acts as a storage polymer in cereals and tubers. These abundant and natural polymers can be used to create high performance nanocomposites presenting outstanding properties. Aqueous suspensions of crystallites can be prepared by acid hydrolysis of the purified substrates. The object of this treatment is to dissolve away regions of low lateral order so that the water-insoluble, highly crystalline residue may be converted into a stable suspension by subsequent vigorous mechanical shearing action. For cellulose and chitin, these monocrystals appear as rod-like nanoparticles which dimensions depend on the biological source of the substrate. In the case of starch they consist of platelet-like nanoparticles. High reinforcing capability was reported resulting from the intrinsic chemical nature of these polymers and from their hierarchical structure. During the last decade, many works have been devoted to mimic biocomposites by blending cellulose whiskers from different sources with polymer matrices.

A biocompatible hydrogel with a double-membrane structure is developed from cationic cellulose nanocrystals (CNC) and anionic alginate. The architecture of the double-membrane hydrogel involves an external membrane composed of neat alginate, and an internal composite hydrogel consolidates by electrostatic interactions between cationic CNC and anionic alginate. The thickness of the outer layer can be regulated by the adsorption duration of neat alginate, and the shape of the inner layer can directly determine the morphology and dimensions of the double-membrane hydrogel (microsphere, capsule, and filmlike shapes). Two drugs are introduced into the different membranes of the hydrogel, which will ensure the complexing drugs codelivery and the varied drugs release behaviors from two membranes (rapid drug release of the outer hydrogel, and prolonged drug release of the inner hydrogel). The double-membrane hydrogel containing the chemically modified cellulose nanocrystals (CCNC) in the inner membrane hydrogel can provide the sustained drug release ascribed to the "nano-obstruction effect" and "nanolocking effect" induced by the presence of CCNC components in the hydrogels. Derived from natural polysaccharides (cellulose and alginate), the novel double-membrane structure hydrogel material developed in this study is biocompatible and can realize the complexing drugs release with the first quick release of one drug and the successively slow release of another drug, which is expected to achieve the synergistic release effects or potentially provide the solution to drug resistance in biomedical application.

A huge variety of plants are harvested worldwide and their different constituents can be converted into a broad range of bionanomaterials. In parallel, much research effort in materials science and engineering is focused on the formation of nanoparticles and nanostructured materials originating from agricultural residues. Cellulose (40-50%), hemicellulose (20-40%), and lignin (20-30%) represent major plant ingredients and many techniques have been described that separate the main plant components for the synthesis of nanocelluloses, nano-hemicelluloses, and nanolignins with divergent and controllable properties. The minor components, such as essential oils, could also be used to produce non-toxic metal and metal oxide nanoparticles with high bioavailability, biocompatibility, and/or bioactivity. This review describes the chemical structure, the physical and chemical properties of plant cell constituents, different techniques for the synthesis of nanocelluloses, nanohemicelluloses, and nanolignins from various lignocellulose sources and agricultural residues, and the extraction of volatile oils from plants as well as their use in metal and metal oxide nanoparticle production and emulsion preparation. Furthermore, details about the formation of activated carbon nanomaterials by thermal treatment of lignocellulose materials, a few examples of mineral extraction from agriculture waste for nanoparticle fabrication, and the emerging applications of plant-based nanomaterials in different fields, such as biotechnology and medicine, environment protection, environmental remediation, or energy production and storage, are also included. This review also briefly discusses the recent developments and challenges of obtaining nanomaterials from plant residues, and the issues surrounding toxicity and regulation.

Metallized paper is patterned to create touch pads of arrayed buttons that are sensitive to contact with both bare and gloved fingers. The paper-based keypad detects the change in capacitance associated with the touch of a finger to one of its buttons. Mounted on an alarmed cardboard box, the keypad requires the appropriate sequence of touches to disarm the system. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Lithium-conducting nanocomposite polymer electrolytes based on high molecular weight poly(oxyethylene) (POE) were prepared from high aspect ratio cellulosic whiskers and lithium imide LiTFSI salt. The thermomechanical behavior of the resulting films was investigated by differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical analysis. The ionic conductivity and the electrochemical stability of the nanocomposite polymer electrolytes are quite consistent with the specifications of lithium batteries. The ionic mobilities were determined by pulsed magnetic field gradient NMR, and it was shown that the reinforcement does not affect the lithium transference number. High performance nanocomposite electrolytes based on tunicin whiskers were obtained. Indeed, the filler provides a high reinforcing effect, while a high level of ionic conductivity is retained with respect to unfilled polymer electrolytes.

The present study has revealed that torrefied coffee grounds (CG) derived from agriculture commodities can be used as bioreinforcing agent for biodegradable poly(butylene adipate-co-terephthalate) (PBAT) without requiring a compatibilizer. The optimum torrefaction operation was achieved in order to increase the hydrophobicity of CG. The raw CG was also used as a reference to assess the effect of the torrefaction operation. The structure and morphology of the composites were examined by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The effect of the addition of raw or torrefied CG on the melting temperature and crystallinity of PBAT biocomposites was analyzed by differential scanning calorimetry (DSC). A significant enhancement in the thermo-mechanical properties for PBAT/torrefied CG composites was observed compared to PBAT/CG composites. Moreover, the hydrophobicity of PBAT composites which was determined by water contact angle was improved when torrefied biomass was added. The thermal stability of the investigated samples was analyzed by thermogravimetric analysis (TGA) and a kinetic model was proposed to describe the thermal degradation of raw CG, torrefied CG, PBAT, and their filled composites. The obtained results for these solvent-free prepared biocomposites show that they can be potential candidates for food packaging applications.