Investigations on sub-structures within cavities of surface imprinted polymers using AFM and PF-QNM.

Investigations on lithographically formed cavities of surface-imprinted polymers (SIP) can help to gain deeper understanding on cell recognition with SIPs: it is known that surface topography and biomolecules transferred during surface imprinting contribute to cell adhesion. In this work, SIPs synthesized via two different imprinting techniques, namely stamp imprinting and polymerization of Pickering emulsions, were investigated and compared to each other, using atomic force microscopy (AFM) and Peak Force Quantitative Nano Mechanics (PF-QNM). We focused on SIPs based on poly(styrene-co-divinylbenzene) as model polymer and E. coli as model template for cell imprinting. Both imprinting approaches led to cavities that revealed nanostructures within the imprints. Stamp imprinting cavities feature low surface roughness and channel structures that resemble the negative pattern of the bacteria on the stamp and their filaments, while SIPs synthesized via polymerization of Pickering emulsions reveal globular nanostructures accumulating in the imprints. AFM phase imaging and adhesion mapping using PF-QNM show that these globular structures are remainders of the imprinted E. coli cells, most likely lipopolysaccarides, which is not observable in imprints resulting from stamp imprinting.

Environmental life cycle assessment of nano-cellulose and biogas production from manure.

Due to its unique properties, nano fibrillated cellulose (NFC) has been a popular topic of research in recent years. Nevertheless, literature assessing environmental impacts of NFC production is scarce, especially for using other starting materials than wood pulp. Hence, in this study, a new approach of cascaded use of manure to produce biogas and subsequently use the cellulose containing digestate for NFC production (manure scenario) is compared to the production from Kraft pulp from hardwood chips (wood chips scenario) via life cycle assessment (LCA). To produce comparable outputs (NFC and biogas) in both scenarios a typical Austrian biogas plant with maize silage and pig slurry as input material is included in the wood chips scenario. A proxy approach is used to upscale the manure scenario from laboratory to an industrial scale (except for the pulp to NFC step) to ensure comparability of both scenarios. The impact categories global warming potential (GWP), fossil resource scarcity, freshwater eutrophication, human toxicity, terrestrial acidification (TAP) and terrestrial ecotoxicity potential are analysed referring to the functional unit of 1 kg NFC. Results show that the manure scenario has at least 45% lower impacts in all assessed categories. GWP is 4.41 kg CO2 eq./kg NFC in the manure and 9.74 kg CO2 eq./kg NFC in the wood chips scenario. The transformation step from pulp to NFC is identified as environmental hotspot due to the high electricity demand in both scenarios. Results are additionally assessed only for the industrial scale part (includes biogas and pulp production). In the latter the main difference can be found in the substrate production. While it plays a subordinate role in the manure scenario (up to 8%) as manure is seen as a waste stream with no upstream environmental impacts attached, the production of maize silage is one of the hotspots in the industrial part in the wood chips scenario. This difference is especially prominent in TAP, where the substrate production is responsible for 91% of the 0.06 kg SO2 eq. impact, which is tenfold the impact of the manure scenario. This underlines the issue of using energy crops as substrate in biogas plants. It also highlights the importance of further research of using waste streams as inputs for the electricity production and subsequent use in the pulp and paper industry. This LCA demonstrates that NFC production from manure is a sustainable alternative to the production from hardwood Kraft pulp.

Nanomaterials Derived from Fungal Sources-Is It the New Hype?

Greener alternatives to synthetic polymers are constantly being investigated and sought after. Chitin is a natural polysaccharide that gives structural support to crustacean shells, insect exoskeletons, and fungal cell walls. Like cellulose, chitin resides in nanosized structural elements that can be isolated as nanofibers and nanocrystals by various top-down approaches, targeted at disintegrating the native construct. Chitin has, however, been largely overshadowed by cellulose when discussing the materials aspects of the nanosized components. This Perspective presents a thorough overview of chitin-related materials research with an analytical focus on nanocomposites and nanopapers. The red line running through the text emphasizes the use of fungal chitin that represents several advantages over the more popular crustacean sources, particularly in terms of nanofiber isolation from the native matrix. In addition, many ß-glucans are preserved in chitin upon its isolation from the fungal matrix, enabling new horizons for various engineering solutions.

High-Performance Polymer Foams by Thermally Induced Phase Separation.

Macroporous, low-density polyetheretherketone, polyetherketoneketone, and polyetherimide foams are produced using a high-temperature, thermally induced phase separation method. A high-boiling-point solvent, which is suitable to dissolve at least 20 wt% of these high-performance polymers at temperatures above 250 °C, is identified. The foam morphology is controlled by the cooling procedure. The resulting polymer foams have porosities close to 80% with surface areas up to 140 m2 g-1 and elastic moduli up to 97 MPa.

Crab vs. Mushroom: A Review of Crustacean and Fungal Chitin in Wound Treatment.

Chitin and its derivative chitosan are popular constituents in wound-treatment technologies due to their nanoscale fibrous morphology and attractive biomedical properties that accelerate healing and reduce scarring. These abundant natural polymers found in arthropod exoskeletons and fungal cell walls affect almost every phase of the healing process, acting as hemostatic and antibacterial agents that also support cell proliferation and attachment. However, key differences exist in the structure, properties, processing, and associated polymers of fungal and arthropod chitin, affecting their respective application to wound treatment. High purity crustacean-derived chitin and chitosan have been widely investigated for wound-treatment applications, with research incorporating chemically modified chitosan derivatives and advanced nanocomposite dressings utilizing biocompatible additives, such as natural polysaccharides, mineral clays, and metal nanoparticles used to achieve excellent mechanical and biomedical properties. Conversely, fungi-derived chitin is covalently decorated with -glucan and has received less research interest despite its mass production potential, simple extraction process, variations in chitin and associated polymer content, and the established healing properties of fungal exopolysaccharides. This review investigates the proven biomedical properties of both fungal- and crustacean-derived chitin and chitosan, their healing mechanisms, and their potential to advance modern wound-treatment methods through further research and practical application.

Waste-Derived Low-Cost Mycelium Nanopapers with Tunable Mechanical and Surface Properties.

Mycelium, the vegetative growth of filamentous fungi, has attracted increasing commercial and academic interest in recent years because of its ability to upcycle agricultural and industrial wastes into low-cost, sustainable composite materials. However, mycelium composites typically exhibit foam-like mechanical properties, primarily originating from their weak organic filler constituents. Fungal growth can be alternatively utilized as a low-cost method for on-demand generation of natural nanofibrils, such as chitin and chitosan, which can be grown and isolated from liquid wastes and byproducts in the form of fungal microfilaments. This study characterized polymer extracts and nanopapers produced from a common mushroom reference and various species of fungal mycelium grown on sugarcane byproduct molasses. Polymer yields of ∼10-26% were achieved, which are comparable to those of crustacean-derived chitin, and the nanopapers produced exhibited much higher tensile strengths than the existing mycelium materials, with values of up to ∼25 MPa (mycelium) and ∼98 MPa (mushroom), in addition to useful hydrophobic surface properties resulting from the presence of organic lipid residues in the nanopapers. HCl or H2O2 treatments were used to remove these impurities facilitating tuning of mechanical, thermal, and surface properties of the nanopapers produced. This potentially enables their use in a wide range of applications including coatings, membranes, packaging, and paper.

Better together: synergy in nanocellulose blends.

Cellulose nanopapers have gained significant attention in recent years as large-scale reinforcement for high-loading cellulose nanocomposites, substrates for printed electronics and filter nanopapers for water treatment. The mechanical properties of nanopapers are of fundamental importance for all these applications. Cellulose nanopapers can simply be prepared by filtering a suspension of nanocellulose, followed by heat consolidation. It was already demonstrated that the mechanical properties of cellulose nanopapers can be tailored by the fineness of the fibrils used or by modifying nanocellulose fibrils for instance by polymer adsorption, but nanocellulose blends remain underexplored. In this work, we show that the mechanical and physical properties of cellulose nanopapers can be tuned by creating nanopapers from blends of various grades of nanocellulose, i.e. (mechanically refined) bacterial cellulose or cellulose nanofibrils extracted from never-dried bleached softwood pulp by chemical and mechanical pre-treatments. We found that nanopapers made from blends of two or three nanocellulose grades show synergistic effects resulting in improved stiffness, strength, ductility, toughness and physical properties.This article is part of a discussion meeting issue 'New horizons for cellulose nanotechnology'.

Recombinant biosynthesis of bacterial cellulose in genetically modified Escherichia coli.

Bacterial cellulose (BC) exhibits unique properties such as high purity compared to plant-based cellulose; however, commercial production of BC has remained a challenge, primarily due to the strain properties of cellulose-producing bacteria. Herein, we developed a functional and stable BC production system in genetically modified (GM) Escherichia coli by recombinant expression of both the BC synthase operon (bcsABCD) and the upstream operon (cmcax, ccp Ax). BC production was achieved in GM HMS174 (DE3) and in GM C41 (DE3) by optimization of the culture temperature (22 °C, 30 °C, and 37 °C) and IPTG concentration. BC biosynthesis was detected much earlier in GM C41 (DE3) cultures (3 h after IPTG induction) than those of Gluconacetobacter hansenii. GM HMS174 (DE3) produced dense fibres having a length of approximately 1000-3000 µm and a diameter of 10-20 µm, which were remarkably larger than the fibres of BC typically produced by G. hansenii.

Emulsion and Foam Templating-Promising Routes to Tailor-Made Porous Polymers.

Emulsions, foams, and foamed emulsions have been used successfully as templates for the synthesis of macroporous polymers. Based on this knowledge this Minireview presents strategies to use, optimise, and upscale these templating methods to synthesise tailor-made porous polymers. The uniqueness of such polymers lies in the ability to tailor their structures and, therefore, their properties. However, systematic studies on structure-property relations are lacking mainly because the templating scientific community is "split into two": the polydisperse and monodisperse camps. Thus, it is time to build a bridge between the camps, that is, to synthesise porous polymers with very different structures from the same precursors to determine the relationship between the structure and the properties.

Noncovalent Surface Modification of Cellulose Nanopapers by Adsorption of Polymers from Aprotic Solvents.

Basic adsorption of hydrophobic polymers from aprotic solvents was introduced as a platform technology to modify exclusively the surfaces of cellulose nanopapers. Dynamic vapor sorption demonstrated that the water vapor uptake ability of the nanopapers remained unperturbed, despite strong repellency to liquid water caused by the adsorbed hydrophobic polymer on the surface. This was enabled by the fact that the aprotic solvents used for adsorption did not swell the nanopaper unlike water that is generally applied as the adsorption medium in such systems. As case examples, the adsorptions of polystyrene (PS) and poly(trifluoroethylene) (PF3E) were followed by X-ray photoelectron spectroscopy and water contact angle measurements, backed up with morphological analysis by atomic force microscopy. The resulting nanopapers are useful in applications like moisture buffers where repellence to liquid water and ability for moisture sorption are desired qualities.

Cellulose nanocrystals by acid vapour: towards more effortless isolation of cellulose nanocrystals.

Cellulose nanocrystals (CNCs) are topical in materials science but their full potential is yet to be fulfilled because of bottlenecks in the production: the process consumes huge amounts of water, recycling the strong acid catalyst is difficult, and purification steps are cumbersome, particularly with lengthy dialysis. Production of CNCs with HCl vapour overcomes many of these difficulties but the dispersion of CNCs from the already hydrolysed fibre matrix is a formidable challenge. This study is a fundamental effort to explore very basic means to facilitate CNC dispersion from cotton linter fibres (filter paper), hydrolysed to levelling off degree of polymerization by HCl vapour. The introduction of carboxylic groups on the cellulose crystal surface proved the most efficient method to alleviate dispersion with good yields (ca. 50%) and a provisional possibility to tune the CNC length. By contrast, attempts to directly disperse untreated hydrolysed fibres in various organic solvents and aqueous surfactant solutions were unsuccessful. The results showed that hydrolysis of native cellulose fibres by HCl vapour is indeed a viable method for producing CNCs but it has more potential as a pre-treatment step rather than a full-fledged process on its own.

Applying a potential difference to minimise damage to carbon fibres during carbon nanotube grafting by chemical vapour deposition.

The application of an in situ potential difference between carbon fibres and a graphite foil counter electrode (300 V, generating an electric field ca 0.3-0.7 V µm-1), during the chemical vapour deposition synthesis of carbon nanotube (CNT) grafted carbon fibres, significantly improves the uniformity of growth without reducing the tensile properties of the underlying carbon fibres. Grafted CNTs with diameters 55 nm ± 36 nm and lengths around 10 µm were well attached to the carbon fibre surface, and were grown without the requirement for protective barrier coatings. The grafted CNTs increased the surface area to 185 m2 g-1 compared to the as-received sized carbon fibre 0.24 m2 g-1. The approach is not restricted to batch systems and has the potential to improve CNT grafted carbon fibre production for continuous processing.

Understanding the Dispersion and Assembly of Bacterial Cellulose in Organic Solvents.

The constituent nanofibrils of bacterial cellulose are of interest to many researchers because of their purity and excellent mechanical properties. Mechanisms to disrupt the network structure of bacterial cellulose (BC) to isolate bacterial cellulose nanofibrils (BCN) are limited. This work focuses on liquid-phase dispersions of BCN in a range of organic solvents. It builds on work to disperse similarly intractable nanomaterials, such as single-walled carbon nanotubes, where optimum dispersion is seen for solvents whose surface energies are close to the surface energy of the nanomaterial; bacterial cellulose is shown to disperse in a similar fashion. Inverse gas chromatography was used to determine the surface energy of bacterial cellulose, under relevant conditions, by quantifying the surface heterogeneity of the material as a function of coverage. Films of pure BCN were prepared from dispersions in a range of solvents; the extent of BCN exfoliation is shown to have a strong effect on the mechanical properties of BC films and to fit models based on the volumetric density of nanofibril junctions. Such control offers new routes to producing robust cellulose films of bacterial cellulose nanofibrils.

Injectable, interconnected, high-porosity macroporous biocompatible gelatin scaffolds made by surfactant-free emulsion templating.

High-porosity interconnected, thermoresponsive macroporous hydrogels are prepared from oil-in-water high internal phase emulsions (HIPEs) stabilized by gelatin-graft-poly(N-isopropylacrylamide). PolyHIPEs are obtained by gelling HIPEs utilizing the thermoresponsiveness of the copolymer components. PolyHIPEs properties can be controlled by varying the aqueous phase composition, internal phase volume ratio, and gelation temperature. PolyHIPEs respond to temperature changes experienced during cell seeding, allowing fibroblasts to spread, proliferate, and penetrate into the scaffold. Encapsulated cells survive ejection of cell-laden hydrogels through a hypodermic needle. This system provides a new strategy for the fabrication of safe injectable biocompatible tissue engineering scaffolds.

Antagonistic effects between magnetite nanoparticles and a hydrophobic surfactant in highly concentrated Pickering emulsions.

Herein we present a systematic study of the antagonistic interaction between magnetite nanoparticles (Fe3O4) and nonionic hydrophobic surfactant in Pickering highly concentrated emulsions. Interfacial tension measurements, phase behavior, and emulsion stability studies, combined with electron microscopy observations in polymerized systems and magnetometry, are used to support the discussion. First, stable W/O highly concentrated emulsions were obtained using partially hydrophobized magnetite nanoparticles. These emulsions experienced phase separation when surfactant is added at concentrations as low as 0.05 wt %. Such phase separation arises from the preferential affinity of the surfactant for the nanoparticle surfaces, which remarkably enhances their hydrophobicity, leading to a gradual desorption of nanoparticles from the interface. W/O emulsions were obtained at higher surfactant concentrations, but in this case, these emulsions were mainly stabilized by surfactant molecules. Therefore, stable emulsions could be prepared in two separate ranges of surfactant concentrations. After polymerization, low-density macroporous polymers were obtained, and the adsorption and aggregation of nanoparticles was analyzed by transmission electron microscopy. The progressive displacement of the nanoparticles was revealed: from the oil-water interface, in which aggregated nanoparticles were adsorbed, forming dense layers, to the continuous phase of the emulsions, where small nanoparticle aggregates were randomly dispersed. Interestingly, the results also show that the blocking temperature of the iron oxide superparamagnetic nanoparticles embedded in the macroporous polymers could be modulated by appropriate control of the concentrations of both surfactant and nanoparticles.

Phase behavior of medium and high internal phase water-in-oil emulsions stabilized solely by hydrophobized bacterial cellulose nanofibrils.

Water-in-oil emulsions stabilized solely by bacterial cellulose nanofibers (BCNs), which were hydrophobized by esterification with organic acids of various chain lengths (acetic acid, C2-; hexanoic acid, C6-; dodecanoic acid, C12-), were produced and characterized. When using freeze-dried C6-BCN and C12-BCN, only a maximum water volume fraction (ϕw) of 60% could be stabilized, while no emulsion was obtained for C2-BCN. However, the maximum ϕw increased to 71%, 81%, and 77% for C2-BCN, C6-BCN, and C12-BCN, respectively, 150 h after the initial emulsification, thereby creating high internal phase water-in-toluene emulsions. The observed time-dependent behavior of these emulsions is consistent with the disentanglement and dispersion of freeze-dried modified BCN bundles into individual nanofibers with time. These emulsions exhibited catastrophic phase separation when ϕw was increased, as opposed to catastrophic phase inversion observed for other Pickering emulsions.

High internal phase emulsion templating with self-emulsifying and thermoresponsive chitosan-graft-PNIPAM-graft-oligoproline.

High internal phase emulsion (HIPE)-templating is an attractive method of producing high porosity polymer foams with tailored pore structure, pore size and porosity. However, this method typically requires the use of large amounts of surfactants to stabilize the immiscible liquid phases, and polymerizable monomers/cross-linker in the continuous minority phase to solidify the HIPE, which may not be desirable in many applications. We show that polyHIPEs with a porosity of 73% can be formed solely using a copolymer of chitosan-graft-PNIPAM-graft-oligoproline (CSN-PRO), which acts simultaneously as emulsifier and thermoresponsive gelator, and forms upon removal of the liquid templating phases, the bulk structure of the resulting polyHIPE. With only a small amount of surfactant (1%v/v in the aqueous phase), and varying the polymer concentration and internal phase volume ratio, different polyHIPEs with porosities of up to 99%, surface areas in excess of 300 m(2)/g and controlled pore interconnectivity can be formed. The poly(CSN-PRO)HIPEs are also shown to be thermoresponsive and remained intact when immersed into water above 34 °C but dissolve below their LCST, which is useful for applications such as drug delivery and tissue engineering scaffolds.

Bacterial cellulose nanopaper as reinforcement for polylactide composites: renewable thermoplastic NanoPaPreg.

Bacterial cellulose (BC) is often regarded as a prime candidate nano-reinforcement for the production of renewable nanocomposites. However, the mechanical performance of most BC nanocomposites is often inferior compared with commercially available polylactide (PLLA). Here, the manufacturing concept of paper-based laminates is used, i.e., "PaPreg," to produce BC nanopaper reinforced PLLA, which has been called "nanoPaPreg" by the authors. It is demon-strated that high-performance nanoPaPreg (vf = 65 vol%) with a tensile modulus and strength of 6.9 ± 0.5 GPa and 125 ± 10 MPa, respectively, can be fabricated. It is also shown that the tensile properties of nanoPaPreg are predominantly governed by the mechanical performance of BC nanopaper instead of the individual BC nanofibers, due to difficulties impregnating the dense nanofibrous BC network.

Flexing with lignin: lignin-based elastomers synthesised from untreated kraft black liquor.

The synthesis and characterisation of a lignin-based elastomer system using lignin-epoxy-resins is presented. Untreated kraft black liquor was used to synthesise glycidyl lignin or black liquor-based epoxy resin (BLER), following a published procedure. A flexible, elastomeric thermoset was produced by cross-linking BLER with succinic anhydride (SA). The produced material was characterised in respect to its chemical, thermal, mechanical and swelling characteristics. In addition, vertical burning tests were performed. The obtained lignin-based elastomeric thermoset had a tensile strength of 1.0 ± 0.20 MPa and elastic moduli of 1.6 ± 1.4 and 0.44 ± 0.35 MPa at 5% and 50% elongation, respectively. A maximum elongation of 151 ± 49% was found.

Functionally Gradient Macroporous Polymers: Emulsion Templating Offers Control over Density, Pore Morphology, and Composition.

Gradient macroporous polymers were produced by polymerization of emulsion templates comprising a continuous monomer phase and an internal aqueous template phase. To produce macroporous polymers with gradient composition, pore size, and foam density, we varied the template formulation, droplet size, and internal phase ratio of emulsion templates continuously and stacked those prior to polymerization. Using the outlined approach, it is possible to vary one property along the resulting macroporous polymer while retaining the other properties. The elastic moduli and crush strengths change along the gradient of the macroporous polymers; their mechanical properties are dominated by those of the weakest layers in the gradient. Macroporous polymers with gradient chemical composition and thus stiffness provide both high impact load and energy adsorption, rendering the gradient foam suitable for impact protective applications. We show that dual-dispensing and simultaneous blending of two different emulsion formulations in various ratios results in a fine, bidirectional change of the template composition, enabling the production of true gradient macroporous polymers with a high degree of design freedom.