Search

A progressively increasing concern about the environmental impacts of the whole polymer industry has boosted the design of less aggressive technologies that allow for the maximum use of carbon atoms, and reduced dependence on the fossil platform. Progresses related to the former approach are mostly based on the concept of the circular economy, which aims at a thorough use of raw materials, from production to disposal. The latter, however, has been considered a priority nowadays, as short-term biological processes can efficiently provide a myriad of chemicals for the polymer industry. Polymers from renewable resources are widely established in research and technology facilities from all over the world, and a broader consolidation of such materials is expected in a near future. Herein, an up-to-date overview of the most recent and relevant contributions dedicated to the production of monomers and polymers from biomass is presented. We provide some basic issues related to the preparation of polymers from renewable resources to discuss ongoing strategies that can be used to achieve original polymers and systems thereof.

This paper provides an overview of the recent progress in research and development dealing with polymers derived from plant oils. It highlights the widening interest in novel approaches to the synthesis, characterization, and properties of these materials from renewable resources and emphasizes their growing impact on sustainable macromolecular science and technology. The monomers used include unmodified triglycerides, their fatty acids or the corresponding esters, and chemically modified triglycerides and fatty acid esters. Comonomers include styrene, divinylbenzene, acrylics, furan derivatives, epoxides, etc. The synthetic pathways adopted for the preparation of these materials are very varied, going from traditional free radical and cationic polymerizations to polycondensation reactions, as well as metatheses and Diels-Alder syntheses. In addition to this general appraisal, the specific topic of the use of tung oil as a source of original polymers, copolymers, and (nano)composites is discussed in greater detail in terms of mechanisms, structures, properties, and possible applications.

The impact of various degrees of acetylation on improving the thermal stability of xylan isolated from different botanical source has been studied; methylglucuronoxylan from birch and eucalyptus, arabinoglucuronoxylan from spruce and glucuronoarabinoxylan from sugarcane bagasse and straw. The lower molecular weight of non- acetylated methylglucuronoxylan (17.7-23.7 kDa) and arabinoglucuronoxylan (16.8 kDa) meant that they were more soluble in water than glucuronoarabinoxylan (43.0-47.0 kDa). The temperature at the onset of degradation increased by 17-61 °C and by 75-145 °C for low and high acetylated xylans respectively, as a result of acetylation. A glass transition temperature in the range of 121-132 °C was observed for the samples non-acetylated and acetylated at low degree of acetylation (0.0-0.6). The acetylation to higher degrees (1.4-1.8) increased the glass transition temperature of the samples to 189-206 °C. Acetylation proved to be an efficient method for functionalization of the xylan to increase the thermal stability., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Complex cellulosic samples are often difficult to analyse with size-exclusion chromatography. The strong molecular associations of hemicelluloses and lignin with cellulose produce multimodal molar mass distributions (MMD) that are difficult to interpret. More reliable ways of calculating the molar masses of cellulose are thus necessary. This is particularly relevant when studying the kinetics of paper degradation, as the number average molar mass is the most precise indicator. In this study various data handling methods based on the deconvolution of bimodal and multimodal MMDs of complex cellulosic samples after SEC-MALS-DRI analysis are examined in order to propose more accurate paper degradation rates. Two deconvolution methods, which do or do not rely on polymer calibration curves were developed and were applied to several kraft and groundwood pulp papers unaged and hygrothermally aged. The deconvolution methods are discussed and evaluated in light of calculated cellulose activation energies, degradation rates and paper usable lifetime predictions., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Due to their compactness and independence of exterior energy sources, capillary microsystems are increasingly used in many different scientific domains, from biotechnology to medicine and biology, chemistry, energy and space. Obtaining a capillary flow depends on channel geometry and contact angle. A general condition for the establishment of a spontaneous capillary flow in a uniform cross section channel has already been derived from Gibbs free energy. In this work, we consider spontaneous capillary flows (SCF) in diverging open rectangular channels and suspended channels, and we show that they do not flow indefinitely but stop at some location in the channel. In the case of linearly diverging open channels, we derive the expression that determines the location where the flow stops. The theoretical approach is verified by using the Surface Evolver numerical program and is checked by experiments. The approach is extended to sudden enlargements, and it is shown that the enlargements can act as stop and trigger valves., (Copyright © 2017 IPEM. Published by Elsevier Ltd. All rights reserved.)

Lignocellulosic materials from municipal solid waste emerge as attractive resources for anaerobic digestion biorefinery. To increase the knowledge required for establishing efficient bioprocesses, dynamics of batch fermentation by the cellulolytic bacterium Ruminiclostridium cellulolyticum were compared using three cellulosic materials, paper handkerchief, cotton discs and Whatman filter paper. Fermentation of paper handkerchief occurred the fastest and resulted in a specific metabolic profile: it resulted in the lowest acetate-to-lactate and acetate-to-ethanol ratios. By shotgun proteomic analyses of paper handkerchief and Whatman paper incubations, 151 proteins with significantly different levels were detected, including 20 of the 65 cellulosomal components, 8 non-cellulosomal CAZymes and 44 distinct extracytoplasmic proteins. Consistent with the specific metabolic profile observed, many enzymes from the central carbon catabolic pathways had higher levels in paper handkerchief incubations. Among the quantified CAZymes and cellulosomal components, 10 endoglucanases mainly from the GH9 families and 7 other cellulosomal subunits had lower levels in paper handkerchief incubations. An in-depth characterization of the materials used showed that the lower levels of endoglucanases in paper handkerchief incubations could hypothetically result from its lower crystallinity index (50%) and degree of polymerization (970). By contrast, the higher hemicellulose rate in paper handkerchief (13.87%) did not result in the enhanced expression of enzyme with xylanase as primary activity, including enzymes from the "xyl-doc" cluster. It suggests the absence, in this material, of molecular structures that specifically lead to xylanase induction. The integrated approach developed in this work shows that subtle differences among cellulosic materials regarding chemical and structural characteristics have significant effects on expressed bacterial functions, in particular the cellulolysis machinery, resulting in different metabolic patterns and degradation dynamics., Competing Interests: We have the following interests: Victor Sabarly and Marc Dubois are employed by Omics Services. This does not alter our adherence to PLOS ONE policies on sharing data and materials.

A mechanistic model of enzymatic hydrolysis taking into account the morphology of the cellulosic particles and its evolution with time was developed. The individual behavior of the main enzymes involved in the reaction (cellobiohydrolases, endoglucanases, and β-glucosidases), as well as synergy effects, were also included. A large panel of experimental tests was done to fit and validate the model. This database included different enzymes mixtures and operating conditions and allowed to determine and compare with accuracy the adsorption and kinetic parameters of the different enzymes. Model predictions on short hydrolysis times were very satisfactory. On longer times, a deactivation constant was added to represent the hydrolysis slowdown. The model also allowed to predict the impact of enzymes ratios and initial substrate parameters (chain length distribution, polymerization degree) on hydrolysis, and to follow the evolution of these parameters with time. This model revealed general trends on the impact of cellulose morphology on hydrolysis. It is a useful tool to better understand the mechanisms involved in enzymatic hydrolysis of cellulose and to determine optimal cellulolytic cocktails for process design., (© 2015 Wiley Periodicals, Inc.)

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.

The industry and consumers are focusing more and more on the development of biodegradable and lightweight food-packaging materials, which could better preserve the quality of the food and improve its shelf-life. In an attempt to meet these requirements, this study presents a novel bio-substrate able to contain active bio-molecules for future food-packaging applications. Based on a paperboard substrate, the development of an antibacterial bio-packaging material is, therein, achieved using a chlorhexidine digluconate (CHX) solution as a model of an antibacterial molecule, mixed with microfibrillated cellulose (MFC) and used as coating onto paperboard samples. AFM and FE-SEM analyses were performed to underline the nanoporous MFC network able to trap and to progressively release the CHX molecules. The release study of CHX was conducted in an aqueous medium and showed a lower proportion (20 %) of CHX released when using MFC. This led to the constant release of low amounts of CHX over 40 h. Antibacterial tests were carried out to assess the preservation of the antibacterial activity of the samples after the release studies. Samples remained active against Bacillus subtilis, with better results being obtained when MFC was used. The preservation of the quality of a model food was finally evaluated paving the way for future promising applications in the food packaging industry.

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., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The aim of this paper is to analyse the effects of the presence of printed electronics on the paper waste streams and specifically on paper recyclability. The analysis is based on a case study focussed on envelopes for postal and courier services provided with these intelligent systems. The smart printed envelope of the study includes a combination of both conventional (thin flexible batteries and resistors) and printed electronic components (conductive track layout based on nanosilver ink). For this purpose, a comparison between envelopes with and without these components (batteries, resistors and conductive track layouts) was carried out through pilot scale paper recycling tests. The generation of rejects during the recycling process as well as the final quality of the recycled paper (mechanical and optical properties) were tested and quantitatively evaluated. The results show that resistors are retained during the screening process in the sieves and consequently they cannot end up in the final screened pulp. Therefore, mechanical and optical properties of the recycled paper are not affected. Nevertheless, inks from the conductive track layouts and batteries were partially dissolved in the process water. These substances were not totally retained in the sieving systems resulting in slight changes in the optical properties of the final recycled paper (variations are 7.2-7.5% in brightness, 8.5-10.7% in whiteness, 1.2-2.2% in L(∗) values, 3.3-3.5% in opacity and 16.1-27% in yellowness). These variations are not in ranges able to cause problems in current paper recycling processes and restrict the use of recycled paper in current applications. Moreover, real impacts on industrial recycling are expected to be even significantly lower since the proportion of paper product with printed circuits in the current paper waste streams are much lower than the ones tested in this work. However, it should be underlined the fact that this situation may change over the next years due to the future developments in printed electronics and the gradual penetration of these types of devices in the market., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The formation of carbonyl groups during the ozone treatment (Z) of eucalyptus (Eucalyptus grandis and Eucalyptus urophylla hybrid) kraft pulps and their behaviors during subsequent alkaline stages were investigated by the CCOA method with carbazole-9-carboxylic acid [2-(2-aminooxethoxy)-ethoxy] amide (CCOA) as the carbonyl-selective fluorescence label. Several pulp samples with or without lignin and hexenuronic acids (hexA) were used to elucidate the effects of these components when present in unbleached kraft pulp. Both hexA and lignin increased the formation of carbonyl groups on cellulose and hemicellulose during ozonation. It was concluded that radicals are likely formed when ozone reacts with either lignin or hexA. These carbonyl groups were involved in cellulose depolymerization during subsequent alkaline extraction stages with sodium hydroxide (E) and alkaline hydrogen peroxide (P, in ZEP or ZP). Their numbers decreased after E but increased during P when H2O2 was not stabilized enough. Several ways to minimize the occurrence of carbonyl group formation are suggested., (Copyright © 2014. Published by Elsevier Ltd.)

In this work, a new use of microfibrillated cellulose (MFC) is highlighted for high-added-value applications. For the first time, a nanoporous network formed by MFC coated on paper is used for a controlled release of molecules. The release study was carried out in water with caffeine as a model molecule. The release process was studied by means of (i) continuous, and (ii) intermittent diffusion experiments (with renewal of the medium every 10 min). The effect of the MFC was first observed for the samples impregnated in the caffeine solution. These samples, coated with MFC (coat weight of about 7 g/m(2)), released the caffeine over a longer period (29 washings compared with 16), even if the continuous diffusions were similar for both samples (without and with MFC coating). The slowest release of caffeine was observed for samples coated with the mixture (MFC+caffeine). Moreover, the caffeine was only fully released 9h after the release from the other samples was completed. This study compared two techniques for the introduction of model molecules in MFC-coated papers. The latter offers a more controlled and gradual release. This new approach creates many opportunities especially in the food-packaging field. A similar study could be carried out with an active species., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The rheological properties of a dispersion of cellulose nanocrystals (CNCs) in an aqueous solution of polyoxyethylene (PEO) have been investigated. A peculiar behavior is reported. Upon adding CNC, the viscosity of the suspension first decreases and then increases. Adsorption of PEO chains on the surface of the nanoparticles has been suspected. Freeze-drying of this PEO-adsorbed CNC dispersion was performed, and the ensuing lyophilizate was extruded with low density polyethylene. Compared to neat CNC-based nanocomposites, both improved dispersibility and thermal stability were observed. This simple and physical method constitutes an approach of choice for the melt processing of CNC-based nanocomposites with a hydrophobic polymeric matrix applicable at the industrial scale.