Fabrication of Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)/ZnO Nanocomposite Films for Active Packaging Applications: Impact of ZnO Type on Structure-Property Dynamics.

Bio-based and biodegradable polyhydroxyalkanoates (PHAs) have great potential as sustainable packaging materials. The incorporation of zinc oxide nanoparticles (ZnO NPs) could further improve their functional properties by providing enhanced barrier and antimicrobial properties, although current literature lacks details on how the characteristics of ZnO influence the structure-property relationships in PHA/ZnO nanocomposites. Therefore, commercial ZnO NPs with different morphologies (rod-like, spherical) and silane surface modification are incorporated into poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) via extrusion and compression molding. All ZnO NPs are homogeneously distributed in the PHBHHx matrix at 1, 3 and 5 wt.%, but finer dispersion is achieved with modified ZnO. No chemical interactions between ZnO and PHBHHx are observed due to a lack of hydroxyl groups on ZnO. The fabricated nanocomposite films retain the flexible properties of PHBHHx with minimal impact of ZnO NPs on crystallization kinetics and the degree of crystallinity (53 to 56%). The opacity gradually increases with ZnO loading, while remaining translucent up to 5 wt.% ZnO and providing an effective UV barrier. Improved oxygen barrier and antibacterial effects against S. aureus are dependent on the intrinsic characteristics of ZnO rather than its morphology. We conclude that PHBHHx retains its favorable processing properties while producing nanocomposite films that are suitable as flexible active packaging materials.

A feasibility study on femtosecond laser texturing of sprayed nanocellulose coatings.

Nanocelluloses are emerging as natural materials with favourable properties for coating industry and can be applied by state-of-the-art spraying technology. While additional functionalities are commonly introduced through chemical modification, the surface microstructuring of nanocellulose coatings with high throughput methods remains unexplored. Here, a femtosecond laser is used for texturing spray-coated coatings made of cellulose nanofibrils (CNF) or cellulose nanocrystals (CNC). For coating thickness of 1.5 to 8 µm, processing limits were determined with maximum ablation energy linearly increasing with coating thickness and minimum ablation energy decreasing or increasing depending on the apparent coating density. Within applicable processing window of pulse rate and power setting, the operational ranges were determined for creating one-dimensional and two-dimensional surface patterns, requiring a higher laser energy for CNC compared to CNF coatings and yielding thinnest possible resolved patterns of 17 µm as determined by the laser spot diameter. The laser ablation under low energy corresponds to an increase in surface roughness and intensifies surface hydrophilicity, while the line patterns are able to pin water droplets with rising water contact angles up to 90°. Present feasibility study opens future possibilities for managing surface properties of nanocellulose coatings in applications where tuning of surface hydrophilicity is required.

High-Temperature Hydrothermal Extraction of Phenolic Compounds from Brewer's Spent Grain and Malt Dust Biomass Using Natural Deep Eutectic Solvents.

Aligned with the EU Sustainable Development Goals 2030 (EU SDG2030), extensive research is dedicated to enhancing the sustainable use of biomass waste for the extraction of pharmaceutical and nutritional compounds, such as (poly-)phenolic compounds (PC). This study proposes an innovative one-step hydrothermal extraction (HTE) at a high temperature (120 °C), utilizing environmentally friendly acidic natural deep eutectic solvents (NADESs) to replace conventional harmful pre-treatment chemicals and organic solvents. Brewer's spent grain (BSG) and novel malt dust (MD) biomass sources, both obtained from beer production, were characterized and studied for their potential as PC sources. HTE, paired with mild acidic malic acid/choline chloride (MA) NADES, was compared against conventional (heated and stirred maceration) and modern (microwave-assisted extraction; MAE) state-of-the-art extraction methods. The quantification of key PC in BSG and MD using liquid chromatography (HPLC) indicated that the combination of elevated temperatures and acidic NADES could provide significant improvements in PC extraction yields ranging from 251% (MD-MAC-MA: 29.3 µg/g; MD-HTE-MA: 103 µg/g) to 381% (BSG-MAC-MA: 78 µg/g; BSG-HTE-MA: 375 µg/g). The superior extraction capacity of MA NADES over non-acidic NADES (glycerol/choline chloride) and a traditional organic solvent mixture (acetone/H2O) could be attributed to in situ acid-catalysed pre-treatment facilitating the release of bound PC from lignin-hemicellulose structures. Qualitative 13C-NMR and pyro-GC-MS analysis was used to verify lignin-hemicellulose breakdown during extraction and the impact of high-temperature MA NADES extraction on the lignin-hemicellulose structure. This in situ acid NADES-catalysed high-temperature pre-treatment during PC extraction offers a potential green pre-treatment for use in cascade valorisation strategies (e.g., lignin valorisation), enabling more intensive usage of available biomass waste stream resources.

Nanocellulose Grades with Different Morphologies and Surface Modification as Additives for Waterborne Epoxy Coatings.

While adding different micro- and nanocellulose types into epoxy coating formulations with waterborne phenalkamine crosslinker, effects on processing conditions and coating performance were systematically investigated. The variations in viscosity, thermal and thermomechanical properties, mechanical behavior, abrasive wear, water contact angles, and coating morphologies were evaluated. The selected additives include microcrystalline cellulose (MCC) at 1 to 10 wt.% and cellulose nanocrystals (CNC), cellulose nanofibers (CNF), cellulose microfibers (CMF), and hydrophobically modified cellulose microfibers (mCMF) at 0.1 to 1.5 wt.%. The viscosity profiles are determined by the inherent additive characteristics with strong shear thinning effects for epoxy/CNF, while the epoxy/mCMF provides lower viscosity and better matrix compatibility owing to the lubrication of encapsulated wax. The crosslinking of epoxy/CNF is favored and postponed for epoxy/(CNC, CMF, mCMF), as the stronger interactions between epoxy and CNF are confirmed by an increase in the glass transition temperature and reduction in the dampening factor. The mechanical properties indicate the highest hardness and impact strength for epoxy/CNF resulting in the lowest abrasion wear rates, but ductility enhances and wear rates mostly reduce for epoxy/mCMF together with hydrophobic protection. In addition, the mechanical reinforcement owing to the specific organization of a nanocellulose network at percolation threshold concentrations of 0.75 wt.% is confirmed by microscopic analysis: the latter results in a 2.6 °C (CNF) or 1.6 °C (CNC) increase in the glass transition temperature, 50% (CNF) or 20% (CNC) increase in the E modulus, 37% (CNF) or 32% (CNC) increase in hardness, and 58% (CNF) or 33% (CNC) lower abrasive wear compared to neat epoxy, while higher concentrations up to 1.5 wt.% mCMF can be added. This research significantly demonstrates that nanocellulose is directly compatible with a waterborne phenalkamine crosslinker and actively contributes to the crosslinking of waterborne epoxy coatings, changing the intrinsic glass transition temperatures and hardness properties, to which mechanical coating performance directly relates.

Role of Bio-Based and Fossil-Based Reactive Diluents in Epoxy Coatings with Amine and Phenalkamine Crosslinker.

The properties of epoxy can be adapted depending on the selection of bio-based diluents and crosslinkers to balance the appropriate viscosity for processing and the resulting mechanical properties for coating applications. This work presents a comprehensive study on the structure-property relationships for epoxy coatings with various diluents of mono-, di-, and bio-based trifunctional glycidyl ethers or bio-based epoxidized soybean oil added in appropriate concentration ranges, in combination with a traditional fossil-based amine or bio-based phenalkamine crosslinker. The viscosity of epoxy resins was already reduced for diluents with simple linear molecular configurations at low concentrations, while higher concentrations of more complex multifunctional diluents were needed for a similar viscosity reduction. The curing kinetics were evaluated through the fitting of data from differential scanning calorimetry to an Arrhenius equation, yielding the lowest activation energies for difunctional diluents in parallel with a balance between viscosity and reactivity. While the variations in curing kinetics with a change in diluent were minor, the phenalkamine crosslinkers resulted in a stronger decrease in activation energy. For cured epoxy resins, the glass transition temperature was determined as an intrinsic parameter that was further related to the mechanical coating performance. Considerable effects of the diluents on coating properties were investigated, mostly showing a reduction in abrasive wear for trifunctional diluents in parallel with the variations in hardness and ductility. The high hydrophobicity for coatings with diluents remained after wear and provided good protection. In conclusion, the coating performance could be related to the intrinsic mechanical properties independently of the fossil- or bio-based origin of diluents and crosslinkers, while additional lubricating properties are presented for vegetable oil diluents.

Benchmark Study of Epoxy Coatings with Selection of Bio-Based Phenalkamine versus Fossil-Based Amine Crosslinkers.

The phenalkamines (PK) derived from cardanol oil can be used as a bio-based crosslinker for epoxy coatings as an alternative for traditional fossil amines (FA). First, the reaction kinetics of an epoxy resin with four PK and FA crosslinkers are compared by differential scanning calorimetry, illustrating a fast reaction rate and higher conversion of PK at room temperature in parallel with a moderate exothermal reaction. Second, the performance of coatings with various concentrations of PK and PK/FA ratios indicates good mixing compatibility between crosslinkers resulting in higher hardness, scratch resistance, hydrophobicity, and abrasive wear resistance of coatings with PK. The superior performance is confirmed over a broad range of resin/crosslinker ratios, facilitating the processing with viscosity profiles depending on the PK type. Although fossil- and bio-based crosslinkers have different chemical structures, the unique linear relationships between intrinsic mechanical properties (i.e., ductility and impact resistance) and coating performance indicate that the degree of crosslinking is a primary parameter controlling coating performance, where PK simultaneously provides high hardness and ductility. In conclusion, the optimization of the processing range for bio-based PK as a crosslinker for epoxy coatings delivers suitable processing conditions and superior mechanical performance compared to traditional amine crosslinkers.

Nanocelluloses as sustainable membrane materials for separation and filtration technologies: Principles, opportunities, and challenges.

Membrane technology is of great interest in various environmental and industrial applications, where membranes are used to separate different mixtures of gas, solid-gas, liquid-gas, liquid-liquid, or liquid-solid. In this context, nanocellulose (NC) membranes can be produced with predefined properties for specific separation and filtration technologies. This review explains the use of nanocellulose membranes as a direct, effective, and sustainable way to solve environmental and industrial problems. The different types of nanocellulose (i.e., nanoparticles, nanocrystals, nanofibers) and their fabrication methods (i.e., mechanical, physical, chemical, mechanochemical, physicochemical, and biological) are discussed. In particular, the structural properties of nanocellulose membranes (i.e., mechanical strength, interactions with various fluids, biocompatibility, hydrophilicity, and biodegradability) are reviewed in relation to membrane performances. Advanced applications of nanocellulose membranes in reverse osmosis (RO), microfiltration (MF), nanofiltration (NF), and ultrafiltration (UF) are highlighted. The applications of nanocellulose membranes offer significant advantages as a key technology for air purification, gas separation, and water treatment, including suspended or soluble solids removal, desalination, or liquid removal using pervaporation membranes or electrically driven membranes. This review will cover the current state of research, future prospects, and challenges in commercializing nanocellulose membranes with respect to membrane applications.

Fabrication of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) Fibers Using Centrifugal Fiber Spinning: Structure, Properties and Application Potential.

Biobased and biodegradable polyhydroxyalkanoates (PHAs) are currently gaining momentum. Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) polymer has a useful processing window for extrusion and injection molding of packaging, agricultural and fishery applications with required flexibility. Processing PHBHHx into fibers using electrospinning or centrifugal fiber spinning (CFS) can further broaden the application area, although CFS remains rather unexplored. In this study, PHBHHx fibers are centrifugally spun from 4-12 wt.% polymer/chloroform solutions. Beads and beads-on-a-string (BOAS) fibrous structures with an average diameter (ϕav) between 0.5 and 1.6 µm form at 4-8 wt.% polymer concentrations, while more continuous fibers (ϕav = 3.6-4.6 µm) with few beads form at 10-12 wt.% polymer concentrations. This change is correlated with increased solution viscosity and enhanced mechanical properties of the fiber mats (strength, stiffness and elongation values range between 1.2-9.4 MPa, 11-93 MPa, and 102-188%, respectively), though the crystallinity degree of the fibers remains constant (33.0-34.3%). In addition, PHBHHx fibers are shown to anneal at 160 °C in a hot press into 10-20 µm compact top-layers on PHBHHx film substrates. We conclude that CFS is a promising novel processing technique for the production of PHBHHx fibers with tunable morphology and properties. Subsequent thermal post-processing as a barrier or active substrate top-layer offers new application potential.

Opportunities for bacterial nanocellulose in biomedical applications: Review on biosynthesis, modification and challenges.

Bacterial nanocellulose (BNC) is a natural polysaccharide produced as extracellular material by bacterial strains and has favorable intrinsic properties for primary use in biomedical applications. In this review, an update on state-of-the art and challenges in BNC production, surface modification and biomedical application is given. Recent insights in biosynthesis allowed for better understanding of governing parameters improving production efficiency. In particular, introduction of different carbon/nitrogen sources from alternative feedstock and industrial upscaling of various production methods is challenging. It is important to have control on the morphology, porosity and forms of BNC depending on biosynthesis conditions, depending on selection of bacterial strains, reactor design, additives and culture conditions. The BNC is intrinsically characterized by high water absorption capacity, good thermal and mechanical stability, biocompatibility and biodegradability to certain extent. However, additional chemical and/or physical surface modifications are required to improve cell compatibility, protein interaction and antimicrobial properties. The novel trends in synthesis include the in-situ culturing of hybrid BNC nanocomposites in combination with organic material, inorganic material or extracellular components. In parallel with toxicity studies, the applications of BNC in wound care, tissue engineering, medical implants, drug delivery systems or carriers for bioactive compounds, and platforms for biosensors are highlighted.

Stabilization of an Aqueous Bio-Based Wax Nano-Emulsion through Encapsulation.

The emulsification of biowaxes in an aqueous environment is important to broaden their application range and make them suitable for incorporation in water-based systems. The study here presented proposes a method for emulsification of carnauba wax by an in-situ imidization reaction of ammonolysed styrene (maleic anhydride), resulting in the encapsulation of the wax into stabilized organic nanoparticles. A parameter study is presented on the influences of wax concentrations (30 to 80 wt.-%) and variation in reaction conditions (degree of imidization) on the stability and morphology of the nanoparticles. Similar studies are done for encapsulation and emulsification of paraffin wax as a reference material. An analytical analysis with Raman spectroscopy and infrared spectroscopy indicated different reactivity of the waxes towards encapsulation, with the bio-based carnauba wax showing better compatibility with the formation of imidized styrene (maleic anhydride) nanoparticles. The latter can be ascribed to the higher functionality of the carnauba wax inducing more interactions with the organic nanoparticle phase compared to paraffin wax. In parallel, the thermal and mechanical stability of nanoparticles with encapsulated carnauba wax is higher than paraffin wax, as studied by differential scanning calorimetry, thermogravimetric analysis and dynamic mechanical analysis. In conclusion, a stable aqueous emulsion with a maximum of 70 wt.-% encapsulated carnauba wax was obtained, being distributed as a droplet phase in 200 nm organic nanoparticles.

Confined Crystallization of Thin Plasma-Polymerized Nanocomposite Films with Maleic Anhydride and Cellulose Nanocrystals under Hydrolysis.

The creation of novel surface morphologies through thin-film patterning is important from a scientific and technological viewpoint in order to control specific surface properties. The pulsed-plasma polymerization of thin nanocomposite films, including maleic anhydride (MA) and cellulose nanocrystals (CNC), may result in different metastable film morphologies that are difficult to control. Alternatively, the transformation of deposited plasma films into crystalline structures introduces unique and more stable morphologies. In this study, the structural rearrangements of plasma-polymerized (MA+CNC) nanocomposite films after controlled hydrolysis in a humid atmosphere were studied, including effects of plasma conditions (low duty cycle, variable power) and monomer composition (ratio MA/CNC) on hydrolysis stability. The progressive growth of crystalline structures with fractal dendrites was observed in confined thin films of 30 to 50 nm. The structures particularly formed on hydrophilic substrates and were not observed before on the more hydrophobic substrates, as they exist as a result of water penetration and interactions at the film/substrate interface. Furthermore, the nucleating effect and local pinning of the crystallites to the substrate near CNC positions enhanced the film stability. The chemical structures after hydrolysis were further examined through XPS, indicating esterification between the MA carboxylic acid groups and CNC surface. The hydrolysis kinetics were quantified from the conversion of anhydride groups into carboxylic moieties by FTIR analysis, indicating enhanced hydrolytic stability of p(MA+CNC) nanocomposite films relative to the pure p(MA) films.

Nanocelluloses as skin biocompatible materials for skincare, cosmetics, and healthcare: Formulations, regulations, and emerging applications.

Nowadays, skin biocompatible products are fast-growing markets for nanocelluloses with increasing number of patents published in last decade. This review highlights recent developments, market trends, safety assessments, and regulations for different nanocellulose types (i.e. nanoparticles, nanocrystals, nanofibers, nanoyarns, bacterial nanocellulose) used in skincare, cosmetics, and healthcare. The specific properties of nanocelluloses for skincare include high viscosity and shear thinning properties, surface functionality, dispersion stability, water-holding capacity, purity, and biocompatibility. Depending on their morphology (e.g. size, aspect ratio, geometry, porosity), nanocelluloses can be used as formulation modifiers, moisturizers, nanofillers, additives, membranes, and films. Nanocellulose composite particles were recently developed as carriers for bioactive compounds or UV-blockers and platforms for wound healing and skin sensors. As toxicological assessment depends on morphologies and intrinsic properties, stringent regulation is needed from the testing of efficient nanocellulose dosages. The challenges and perspectives for an industrial breakthrough are related to optimization of production and processing conditions.

Nanocellulose-Based Materials for Water Treatment: Adsorption, Photocatalytic Degradation, Disinfection, Antifouling, and Nanofiltration.

Nanocelluloses are promising bio-nano-materials for use as water treatment materials in environmental protection and remediation. Over the past decades, they have been integrated via novel nanoengineering approaches for water treatment processes. This review aims at giving an overview of nanocellulose requirements concerning emerging nanotechnologies of waster treatments and purification, i.e., adsorption, absorption, flocculation, photocatalytic degradation, disinfection, antifouling, ultrafiltration, nanofiltration, and reverse osmosis. Firstly, the nanocellulose synthesis methods (mechanical, physical, chemical, and biological), unique properties (sizes, geometries, and surface chemistry) were presented and their use for capturing and removal of wastewater pollutants was explained. Secondly, different chemical modification approaches surface functionalization (with functional groups, polymers, and nanoparticles) for enhancing the surface chemistry of the nanocellulose for enabling the effective removal of specific pollutants (suspended particles, microorganisms, hazardous metals ions, organic dyes, drugs, pesticides fertilizers, and oils) were highlighted. Thirdly, new fabrication approaches (solution casting, thermal treatment, electrospinning, 3D printing) that integrated nanocelluloses (spherical nanoparticles, nanowhiskers, nanofibers) to produce water treatment materials (individual composite nanoparticles, hydrogels, aerogels, sponges, membranes, and nanopapers) were covered. Finally, the major challenges and future perspectives concerning the applications of nanocellulose based materials in water treatment and purification were highlighted.

Extrusion and Injection Molding of Poly(3-Hydroxybutyrate-co-3-Hydroxyhexanoate) (PHBHHx): Influence of Processing Conditions on Mechanical Properties and Microstructure.

Biobased and biodegradable polyhydroxyalkanoates (PHAs) have great potential as sustainable packaging materials. However, improvements in their processing and mechanical properties are necessary. In this work, the influence of melt processing conditions on the mechanical properties and microstructure of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) is examined using a full factorial design of experiments (DoE) approach. We have found that strict control over processing temperature, mold temperature, screw speed, and cooling time leads to highly increased elongation at break values, mainly under influence of higher mold temperatures at 80 °C. Increased elongation of the moldings is attributed to relaxation and decreased orientation of the polymer chains together with a homogeneous microstructure at slower cooling rates. Based on the statistically substantiated models to determine the optimal processing conditions and their effects on microstructure variation and mechanical properties of PHBHHx samples, we conclude that optimizing the processing of this biopolymer can improve the applicability of the material and extend its scope in the realm of flexible packaging applications.

Active Barrier Coating for Packaging Paper with Controlled Release of Sunflower Oils.

The use of paper as a sustainable packaging material is favored, but it lacks sufficient barrier properties in terms of water repellence and oil resistance. Novel approaches consider active packaging materials or coatings with controlled release providing additional functionality for delivery of specific components to the surface. In this study, the development of a waterborne coating with organic nanoparticles and encapsulated sunflower oils is presented as a system for thermal release of the oil and on-demand tuning of the final barrier properties of the paper substrate. After synthesis of the nanoparticles, it seems that the encapsulation of various grades of sunflower oil (i.e., either poly-unsaturated or mono-unsaturated) strongly affects the encapsulation efficiency and thermal release profiles. The water contact angles are controlled by the oil release and chemical surface composition of the coating upon thermal heating. The oil resistance of the paper improves as a more continuous oil film is formed during thermal release. In particular, the chemical surface composition of the paper coatings is detailed by means of micro-Raman spectroscopy and surface imaging, which provide an analytical quantification tool to evaluate surface coverage, oil delivery, and variations in organic coating moieties.

A platform for functionalization of cellulose, chitin/chitosan, alginate with polydopamine: A review on fundamentals and technical applications.

Nature provides concepts and materials with interesting functionalities to be implemented in innovative and sustainable materials. In this review, it is illustrated how the combination of biological macromolecules, i.e. polydopamine and polysaccharides (cellulose, chitin/chitosan, alginate), enables to create functional materials with controlled properties. The mussel-adhesive properties rely on the secretion of proteins having 3,4-dihydroxyphenylalanine amino acid with catechol groups. Fundamental understanding on the biological functionality and interaction mechanisms of dopamine in the mussel foot plaque is presented in parallel with the development of synthetic analogues through extraction or chemical polymer synthesis. Subsequently, modification of cellulose, chitin/chitosan or alginate and their nanoscale structures with polydopamine is discussed for various technical applications, including bio- and nanocomposites, films, filtration or medical membranes, adhesives, aerogels, or hydrogels. The presence of polydopamine stretches far beyond surface adhesive properties, as it can be used as an intermediate to provide additional performance of hydrophobicity, self-healing, antimicrobial, photocatalytic, sensoric, adsorption, biocompatibility, conductivity, coloring or mechanical properties. The dopamine-based 'green' chemistry can be extended towards generalized catechol chemistry for modification of polysaccharides with tannic acid, caffeic acid or laccase-mediated catechol functionalization. Therefore, the modification of polysaccharides with polydopamine or catechol analogues provides a general platform for sustainable material functionalization.

Plant celluloses, hemicelluloses, lignins, and volatile oils for the synthesis of nanoparticles and nanostructured materials.

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.

Engineering the Cellulose Fiber Interface in a Polymer Composite by Mussel-Inspired Adhesive Nanoparticles with Intrinsic Stress-Sensitive Responsivity.

The interface between the fiber and matrix plays a key role in polymer composite performance and is adapted by chemical modification of the fiber surface. In this study, biomimetic adhesive nanoparticles formed by the self-assembly of polymer-peptide amphiphiles with a polydiacetelyene tail and local presentation of 3-hydroxyphenylalanine or DOPA adhesive groups at the outer surface are adsorbed on cellulose fiber surfaces for (i) probing the nanoscale adhesion in combination with a functionalized atomic force microscopy tip and (ii) evaluating the macroscale adhesion by single-fiber pull out tests from a solvent cast cellulose/poly(methyl methacrylate) composite. The interface properties are altered by changing the structure of the nanoparticles into either vesicular or planar shapes depending on the number of incorporated amphiphiles with adhesive groups and the nanoparticle concentration at the cellulose fiber surface. Based on nanoscale adhesive measurements, the adhesion force on modified cellulose fibers increases as a function of the nanoparticle concentration and is higher for the vesicular than for the planar nanoparticle structures. However, the local presentation and number of adhesive groups seems to rule over the surface roughness effects. From macrosale tests, an optimum concentration of adhesive vesicles provides maximum interface strength, while the formation of nanoparticle multilayers at higher concentrations results in lower interface adhesion. In addition, the intrinsic fluorescent properties of the adhesive vesicles under mechanical stress provide a unique tool to evaluate local failure and stress concentrations in the fiber/matrix interface. The incorporation of both adhesive and sensitive properties and versatility of the adhesive functional group may be an attractive strategy for the surface modification of fiber-reinforced composites in general.

Morphology, Rheology and Crystallization in Relation to the Viscosity Ratio of Polystyrene/Polypropylene Polymer Blends.

Microfibrillar and droplet morphology of polypropylene (PP) phase dispersed in polypropylene (PS) was fabricated by using melt-extrusion. This morphology was obtained by introducing isotactic PP (20 wt.%) with different viscosity in the PS matrix (80 wt.%). Furthermore, the rheological properties of the blend investigated as a function of the viscosity ratio K. The variations in blend morphology were related to crystallization, melting properties, and viscoelasticity. The blends with K >> 1 develop a fine morphology with PP microfibrils along the flow direction, while diameters of the dispersed PP droplets gradually increase with lower values of K = 1, or K << 1. Crystallinity of the prepared blends significantly decreases compared to neat PP, while the microfibrillar morphology induces homogeneous crystallization with small crystallites. This is reflected in a decrease of the crystallization temperature, small loss in the crystallinity, and lower melting temperature of the PS80/PP20 blend compared to neat PP. The storage moduli, loss moduli, and complex viscosity are highest for the microfibrillar morphology that presents retarded relaxation. The rheological properties are dominated by the dispersed phase (K > 1), or matrix (K < 1). The variation in blend properties with microfibrillar morphology can be clearly distinguished from heterogeneous blends containing PP droplets, providing an efficient tool to create a binary blend with unique properties.

Fenton-Mediated Biodegradation of Chlorendic Acid - A Highly Chlorinated Organic Pollutant - By Fungi Isolated From a Polluted Site.

Chlorendic acid is a recalcitrant, highly chlorinated organic pollutant for which no microbial degrader has yet been identified. To address this knowledge gap, fungi were isolated from bulk soil, rhizosphere, and roots of the common bent (Agrostis capillaris) and the hybrid poplar [Populus deltoides × (Populus trichocarpa × P. deltoides) cv. Grimminge], both of which grow on a chlorendic acid polluted site in Belgium. Isolates were taxonomically identified and phenotypically screened for chlorendic acid degradation. Several fungal isolates could degrade chlorendic acid in liquid media up to 45%. The chlorendic acid degrading fungal isolates produced higher levels of hydroxyl radicals when exposed to the pollutant when compared to non-exposed controls, suggesting that the oxidative degradation of chlorendic acid occurs through production of Fenton-mediated hydroxyl radicals. In addition, the isolated Ascomycete Penicillium sp. 1D-2a degraded 58% of the original chlorendic acid concentration in the soil after 28 days. This study demonstrates that the presence of fungi in a chlorendic acid polluted soil can degrade this highly chlorinated organic pollutant. These results indicate that recalcitrant, seemingly non-biologically degradable organic pollutants, such as chlorendic acid, can be remediated by using bioremediation, which opens new perspectives for in situ bioremediation.