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The employment of atomic layer deposition and spin coating techniques for preparing inorganic-organic hybrid multilayer structures of alternating ZnO-CNC layers was explored in this study. Helium ion microscopy and X-ray reflectivity showed the superlattice formation for the nanolaminate structures and atomic force microscopy established the efficient control of the CNCs surface coverage on the Al-doped ΖnO by manipulating the concentration of the spin coating solution. Thickness characterization of the hybrid structures was performed via both ellipsometry and X-ray reflectivity and the thermal conductivity was examined by time domain thermoreflectance technique. It appears that even the incorporation of a limited amount of CNCs between the ZnO laminates strongly suppresses the thermal conductivity. Even small, submonolayer amounts of CNCs worked as a more efficient insulating material than hydroquinone or cellulose nanofibers which have been employed in previous studies.

Osmotic dehydration (OD) was introduced as a method to reproducibly tune the water content and porosity of cellulose nanofiber (CNF) hydrogels. The hierarchical porosity was followed by electron microscopy (pores with a >100 μm diameter) and thermoporosimetry (mesopores), together with mechanical testing, in hydrogels with solid contents ranging from 0.7 to 12 wt %. Furthermore, a reciprocal correlation between proton conductivity and the ratio of water bound to the nanocellulose network was established, suggesting the potential of these systems toward tunable energy materials.

The trend to replace petroleum-based products with sustainable alternatives has shifted research efforts toward plant-based materials such as cellulose nanocrystals (CNCs). CNCs show promise in numerous applications (e.g., composites and rheological modifiers); however, maximizing their performance often requires surface modifications with complex chemistries and purification steps. Presented here is a novel surface modification method with the potential to tune CNC properties through the in situ deposition of cellulose phosphate oligosaccharides during CNC production. This was achieved by leveraging the selective solubility of oligosaccharides, which are soluble at a low pH (during the CNC hydrolysis) yet become insoluble and precipitate onto CNC surfaces upon increasing pH during quenching. Oligosaccharide-coated CNCs demonstrated subtle changes including higher surface charge densities and lower water adsorption capacities and viscosities than their unmodified counterparts. CNC surface coverage was tuned by controlling the oligosaccharide degree of polymerization. Overall, this fundamental study introduces an easily scalable modification route that opens the door for expanded CNC functionality and applications.

Funding Information: The financial support of the Austrian Federal Ministry of Digital and Economic Affairs and the National Foundation for Research, Technology and Development , Austria, is gratefully acknowledged. We also thank the industrial partners Mondi, Canon Production Printing, Kelheim Fibres, and SIG Combibloc for their support. Publisher Copyright: © 2021 Copyright: Copyright 2021 Elsevier B.V., All rights reserved. Hydrophobization of cellulosic materials and particularly paper products is a commonly used procedure to render papers more resistant to water and moisture. Here, we explore the hydrophobization of unsized paper sheets via the gas phase. We employed three different compounds, namely palmitoyl chloride (PCl), trifluoroacetic anhydride/acetic anhydride (TFAA/Ac2O)) and hexamethyldisilazane (HMDS) which were vaporized and allowed to react with the paper sheets via the gas phase. All routes yielded hydrophobic papers with static water contact angles far above 90° and indicated the formation of covalent bonds. The PCl and TFAA approach negatively impacted the mechanical and optical properties of the paper leading to a decrease in tensile strength and yellowing of the sheets. The HMDS modified papers did not exhibit any differences regarding relevant paper technological parameters (mechanical properties, optical properties, porosity) compared to the non-modified sheets. XPS studies revealed that the HMDS modified samples have a rather low silicon content, pointing at the formation of submonolayers of trimethylsilyl groups on the fiber surfaces in the paper network. This was further investigated by penetration dynamic analysis using ultrasonication, which revealed that the whole fiber network has been homogeneously modified with the silyl groups and not only the very outer surface as for the PCl and the TFAA modified papers. This procedure yields a possibility to study the influence of hydrophobicity on paper sheets and their network properties without changing structural and mechanical paper parameters.

Cell immobilization is a promising approach to create efficient photosynthetic cell factories for sustainable chemical production. Here, we demonstrate a novel photosynthetic solid-state cell factory design for sustainable biocatalytic ethylene production. We entrapped cyanobacteria within never-dried hydrogel films of TEMPO-oxidized cellulose nanofibers (TCNF) cross-linked with polyvinyl alcohol (PVA) to create a self-standing matrix architecture. The matrix is operational in the challenging submerged conditions and outperforms existing alginate-based solutions in terms of wet strength, long-term cell fitness, and stability. Based on rheological investigations, the critical strength of wet TCNF matrices is three times higher than in the existing immobilization matrices of alginate cross-linked with Ca2+. This is due to the rigid nature of the colloidal nanofiber network and the strong cross-linking with PVA, as opposed to polymeric alginate with reversible ionic Ca2+bonds. The porous and hygroscopic nanofiber network also shields the cyanobacterial cells from environmental stress, maintaining photosynthetic activity during partial drying of films, and when submerged in the nutrient medium for long-term cultivation. Finally, TCNF matrices allow the ethylene-producingSynechocystissp. PCC 6803 cells to operate in submerged conditions under high inorganic carbon loads (200 mM NaHCO3), where Ca2+-alginate matrices fail. The latter show severe cell leakage due to matrix disintegration already within 20 min of NaHCO3supplementation. In contrast, TCNF-based matrices prevent cell leakage to the medium and restrict culture growth, leading to improved ethylene production yields. Furthermore, the operational capacity of the self-standing TNCF cell factory can be maintained long-term by periodically refreshing the nutrient medium. All in all, the results showcase the versatility and potential of cell immobilization with the never-dried colloidal TCNF matrix, paving the way towards novel biotechnological pathways using solid-state cell factories designed for efficient and sustainable production ofe.g., monomers and fuels.

HCl gas hydrolysis of a bacterial cellulose (BC) aerogel followed by 2,2,6,6-tetramethylpiperidine-1-oxyl radical-mediated oxidation was used to produce hydrolyzed BC with carboxylate groups, which subsequently disintegrated into a stable dispersion of cellulose nanocrystals (CNCs). The degree of polymerization was successfully reduced from 2160 to 220 with a CNC yield of >80%.

TEMPO-oxidised cellulose fibres are often explored as nano-reinforcement for polymers. However, it is unclear whether micrometre-sized TEMPO-oxidised cellulose fibres also possess similar reinforcing potential. In this work, we report the mechanical response of polypropylene (PP) composites reinforced with TEMPO-oxidised cellulose (TOC) of different fibre widths. Micrometre-sized TOC fibres (TOCF) containing sodium carboxylate (TOCF-Na) and free hydroxyl (TOCF-H) groups, as well as nano-sized TOC nanofibrils (TOCN) were produced from dissolving pulp and incorporated into PP matrix via melt-extrusion. It was found that model PP composites containing micrometre-sized TOCF-Na and TOCF-H possessed the highest tensile modulus of up to 2.5 GPa; 40% improvement over neat PP and 30% increase over PP/TOCN composite. No significant differences in the tensile strength of PP/TOCF-Na and PP/TOCF-H composites were observed when compared to neat PP. The incorporation of nano-sized TOCN into PP however, led to a 6% decrease in tensile strength. Single-edge notched beam fracture toughness test further showed that PP/TOCN composite possessed the lowest fracture toughness of 2.52 MPa m1/2; a decrease of 18% over PP reinforced with micrometre-sized TOCF-Na and TOCF-H. Our study shows that micrometre-sized TOCFs serve as better reinforcement for polymers compared to nano-sized TOCN. This is attributed to the better dispersion of TOCF in the PP matrix. Furthermore, the presence of surface microfibrillation on TOCFs also enhanced the quality of the TOCF-PP interface through mechanical interlocking and local stiffening of the PP matrix.

The use of chemical and energy intensive delignification processes in industrial pulping generates cellulosic fibres that are hydrophilic, hygroscopic and functionally restricted to paper and cardboard applications. Here, we propose a bio-based alternative to chemical pulping utilising herbivores to harvest and grind lignocellulosic materials followed by natural fungal growth to delignify and hybridise them to generate hierarchical composite papers with altered, water-repelling surface properties. These papers comprise cellulose and fungal biopolymers produced by cultivation of T. versicolor and P. ostreatus on elephant manure. Papers with considerably more hydrophobic surfaces were obtained at glucosamine contents as low as 0.1 wt%. Paper tensile strengths and elastic moduli were improved with longer fungal growth periods, spanning several weeks, resulting in comprehensive interfacing of cellulose microfibrils through tough nanoscale fungal chitin-β-glucan networks within the papers. Papers produced from lignocellulosic material colonised with P. ostreatus for 16 weeks exhibited the highest tensile strengths and more hydrophobic surfaces than T. versicolor. Hybridisation of lignocellulose with fungal biopolymers resulting in improved surface and mechanical properties highlights the extended opportunities of fungal delignification bioprocessing and demonstrates the considerable potential of the fungal biorefinery as an economical, and as of yet underexploited technology.

Herein, we demonstrate an effective approach toward functionalization of cellulose nanocrystal (CNC) reducing ends by means of a Knoevenagel condensation reaction with a reactive β-diketone (acetylacetone). The end-wise modification was elucidated by advanced NMR analysis, which was facilitated by dissolving the CNCs in ionic liquid electrolyte and by the concomitant assignment of a model compound derived from d-cellobiose. The diffusion-edited 1H experiment afforded a simple method to identify the assigned model resonances in the reducing end-modified CNCs. The condensations can be carried out in aqueous bicarbonate solutions, avoiding the use of hazardous solvents. Under these preliminary aqueous conditions, end-group conversion of up to 12.5% could be confirmed. These results demonstrate the potential of β-diketone chemistry and the Knoevenagel condensation for functionalizing cellulose reducing ends. Application of this liquid-state NMR method for confirming and quantifying reducing end conversion is also shown to be invaluable. Extension of this chemistry to other 1,3-dicarbonyl compounds and solvation conditions should allow for the topochemical and (axially) chirotopic installation of functional moieties to CNCs, paving the way to asymmetric cellulose-based nanomaterials with unique properties.

Funding Information: KSK and AB acknowledge funding by the UK Engineering and Physical Sciences Research Council (EPSRC) (EP/K014676/1). KSK also acknowledges Academy of Finland (Project number 310943). EK is grateful for the support by the FinnCERES Materials Bioeconomy Ecosystem. Funding Information: Open access funding provided by Aalto University. KSK and AB acknowledge funding by the UK Engineering and Physical Sciences Research Council (EPSRC) (EP/K014676/1). KSK also acknowledges Academy of Finland (Project number 310943). Publisher Copyright: © 2021, The Author(s). Copyright: Copyright 2021 Elsevier B.V., All rights reserved. Cellulose nanopapers provide diverse, strong and lightweight templates prepared entirely from sustainable raw materials, cellulose nanofibers (CNFs). Yet the strength of CNFs has not been fully capitalized in the resulting nanopapers and the relative influence of CNF strength, their bonding, and biological origin to nanopaper strength are unknown. Here, we show that basic principles from paper physics can be applied to CNF nanopapers to illuminate those relationships. Importantly, it appeared that ~ 200 MPa was the theoretical maximum for nanopapers with random fibril orientation. Furthermore, we demonstrate the contrast in tensile strength for nanopapers prepared from bacterial cellulose (BC) and wood-based nanofibrillated cellulose (NFC). Endemic amorphous polysaccharides (hemicelluloses) in NFC act as matrix in NFC nanopapers, strengthening the bonding between CNFs just like it improves the bonding between CNFs in the primary cell wall of plants. The conclusions apply to all composites containing non-wovenfiber mats as reinforcement.

Funding Information: We gratefully thank the Academy of Finland (project nos. 308578, 303804, and 267497), Jane and Aatos Erkko Foundation, Sigrid Jus?lius Foundation, and Emil Aaltonen Foundation for financial support. FinnCERES Academy of Finland Flagship programme (project numbers 318891) is acknowledged for FTIR, AFM and QCM-D. This work was carried out under the Academy of Finland's Centers of Excellence Programme (2014-2019). Funding Information: We gratefully thank the Academy of Finland (project nos. 308578, 303804, and 267497), Jane and Aatos Erkko Foundation, Sigrid Jusélius Foundation, and Emil Aaltonen Foundation for financial support. FinnCERES Academy of Finland Flagship programme (project numbers 318891) is acknowledged for FTIR, AFM and QCM-D. This work was carried out under the Academy of Finland’s Centers of Excellence Programme (2014-2019). Publisher Copyright: © 2021 The Author(s) Copyright: Copyright 2021 Elsevier B.V., All rights reserved. Heparin is one of the most important anticoagulant agents used in clinical applications. Commercial heparin production includes an isolation from mucosa and an additional enrichment step by cationic resins. However, this process remains time-consuming while heparin is obtained in very low concentrations with the presence of macromolecular impurities, such as proteins. Therefore, an alternative with a fast, efficient and selective heparin-recovery performance is highly desirable. In this work, we utilized a biomass-derived cellulose nanocrystal colloid conjugated with cationic polyelectrolytes for heparin recovery. The high specific surface area and brush-like structure significantly increased the heparin-capture speed and efficiency under physiologically relevant conditions, which were demonstrated by the methylene blue binding assay and quartz crystal microbalance measurement. We also found that a selective heparin capture can be realized via adjusting salt concentration or pH. Finally, we showed that after several recycle rounds, the heparin-recovery ability of the cationic nanocrystals was largely retained and the majority of active heparin dose was recovered, showing a significantly higher heparin-recovery performance than the commercial Amberlite IRA-900 and demonstrating its applicability from an economic perspective. Therefore, the reported cellulose nanocrystal-polymer conjugate represents a promising candidate for a green and efficient heparin recovery.

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 β-glucans are preserved in chitin upon its isolation from the fungal matrix, enabling new horizons for various engineering solutions.

Cellulose carbamate (CC) was employed as a water-soluble precursor in the manufacturing of cellulose based thin films using the spin coating technique. An intriguing observation was that during spin coating of CC from alkaline aqueous solutions, regeneration to cellulose was accomplished without the addition of any further chemicals. After rinsing, homogeneous thin films with tunable layer thickness in a range between 20 and 80 nm were obtained. Further, CC was blended with cellulose xanthate in different ratios (3:1, 1:1, 1:3) and after regeneration the properties of the resulting all-cellulose blend thin films were investigated. We could observe some slight indications of phase separation by means of atomic force microscopy. The layer thickness of the blend thin films was nearly independent of the ratio of the components, with values between 50 and 60 nm for the chosen conditions. The water uptake capability (80-90% relative to the film mass) determined by H2O/D2O exchange in a quartz crystal microbalance was independent of the blend ratio.

Funding Information: I.S. thanks The Academy of Finland (grant no. 300364) for funding this work. C.D. acknowledges funding from FAPESP (grant 13/07932‐6). P.A.P. thanks the Emil Aaltonen Foundation and Academy of Finland (grant no. 315768) for funding and ESRF for beamtime at beamline D2am (experiment 02‐01‐885). Rita Hatakka is acknowledged for her assistance with the GPC measurements. Work of M.L. was supported by the Jane and Aatos Erkko Foundation. The work is a part of the FinnCERES Bioeconomy ecosystem. Publisher Copyright: © 2021 The Authors. Macromolecular Rapid Communications published by Wiley-VCH GmbH Copyright: Copyright 2021 Elsevier B.V., All rights reserved. Nanoparticle assembly is intensely surveyed because of the numerous applications within fields such as catalysis, batteries, and biomedicine. Here, directed assembly of rod-like, biologically derived cellulose nanocrystals (CNCs) within the template of a processed cotton fiber cell wall, that is, the native origin of CNCs, is reported. It is a system where the assembly takes place in solid state simultaneously with the top-down formation of the CNCs via hydrolysis with HCl vapor. Upon hydrolysis, cellulose microfibrils in the fiber break down to CNCs that then pack together, resulting in reduced pore size distribution of the original fiber. The denser packing is demonstrated by N2 adsorption, water uptake, thermoporometry, and small-angle X-ray scattering, and hypothetically assigned to attractive van der Waals interactions between the CNCs.

Funding Information: This work was part of the Academy of Finland’s Flagship Program (Project Numbers 318890 and 318891, Competence Center for Materials Bioeconomy, FinnCERES). K.H. acknowledges postdoc funding provided by the Academy of Finland (Project Number 333905). A.K. and T.K. would like to acknowledge the Academy of Finland for funding under the project “WTF-Click-Nano” (Project #311255). G.D. and J.Z. acknowledge funding provided by the Swiss National Science Foundation (SNSF; Ambizione Grant No. PZ00P2_167900), and G.D., C.W., and J.Z. thank the Adolphe Merkle Foundation for support. J.Z. gratefully acknowledges the Serra Hunter Fellowship from the Generalitat de Catalunya. Publisher Copyright: © When cellulose nanocrystals (CNCs) are isolated from cellulose microfibrils, the parallel arrangement of the cellulose chains in the crystalline domains is retained so that all reducing end-groups (REGs) point to one crystallite end. This permits the selective chemical modification of one end of the CNCs. In this study, two reaction pathways are compared to selectively attach atom-transfer radical polymerization (ATRP) initiators to the REGs of CNCs, using reductive amination. This modification further enabled the site-specific grafting of the anionic polyelectrolyte poly(sodium 4-styrenesulfonate) (PSS) from the CNCs. Different analytical methods, including colorimetry and solution-state NMR analysis, were combined to confirm the REG-modification with ATRP-initiators and PSS. The achieved grafting yield was low due to either a limited conversion of the CNC REGs or side reactions on the polymerization initiator during the reductive amination. The end-tethered CNCs were easy to redisperse in water after freeze-drying, and the shear birefringence of colloidal suspensions is maintained after this process.

Cellulose hydrolysis is an extensively studied process due to its relevance in the fields of biofuels, chemicals production, and renewable nanomaterials. However, the direct visualization of the process accompanied with detailed scaling has not been reported because of the vast morphological alterations occurring in cellulosic fibers in typical heterogeneous (solid/liquid) hydrolytic systems. Here, we overcome this distraction by exposing hardwood cellulose nanofibers (CNFs) deposited on silica substrates to pressurized HCl gas in a solid/gas system and examine the changes in individual CNFs by atomic force microscopy (AFM). The results revealed that hydrolysis proceeds via an intermediate semi-fibrous stage before objects reminiscent of cellulose nanocrystals were formed. The length of the nanocrystal-like objects correlated well with molar mass, as analyzed by gel permeation chromatography, performed on CNF aerogels hydrolyzed under identical conditions. Meanwhile, X-ray diffraction showed a slight increasein crystallinity index as the hydrolysis proceeded. The results provide a modern visual complement to >100 years of research in cellulose degradation.

openaire: EC/H2020/742829/EU//DRIVEN In the effort toward sustainable advanced functional materials, nanocelluloses have attracted extensive recent attention. Nanocelluloses range from rod-like highly crystalline cellulose nanocrystals to longer and more entangled cellulose nanofibers, earlier denoted also as microfibrillated celluloses and bacterial cellulose. In recent years, they have spurred research toward a wide range of applications, ranging from nanocomposites, viscosity modifiers, films, barrier layers, fibers, structural color, gels, aerogels and foams, and energy applications, until filtering membranes, to name a few. Still, nanocelluloses continue to show surprisingly high challenges to master their interactions and tailorability to allow well-controlled assemblies for functional materials. Rather than trying to review the already extensive nanocellulose literature at large, here selected aspects of the recent progress are the focus. Water interactions, which are central for processing for the functional properties, are discussed first. Then advanced hybrid gels toward (multi)stimuli responses, shape-memory materials, self-healing, adhesion and gluing, biological scaffolding, and forensic applications are discussed. Finally, composite fibers are discussed, as well as nanocellulose as a strategy for improvement of photosynthesis-based chemicals production. In summary, selected perspectives toward new directions for sustainable high-tech functional materials science based on nanocelluloses are described.

Native plant cellulose has an intrinsic supramolecular structure. Consequently, it can be isolated as nanocellulose species, which can be utilized as building blocks for renewable nanomaterials. The structure of cellulose also permits its end‐wise modification, i.e., chemical reactions exclusively on one end of a cellulose chain or a nanocellulose particle. The premises for end‐wise modification have been known for decades. Nevertheless, different approaches for the reactions have emerged only recently, because of formidable synthetic and analytical challenges associated with the issue, including the adverse reactivity of the cellulose reducing end and the low abundance of newly introduced functionalities. This Review gives a full account of the scientific underpinnings and challenges related to end‐wise modification of cellulose nanocrystals. Furthermore, we present how the chemical modification of cellulose nanocrystal ends may be applied to directed assembly, resulting in numerous possibilities for the construction of new materials, such as responsive liquid crystal templates and composites with tailored interactions., Topochemical modifications at the reducing end of nanocellulose are a new trend in cellulose materials research. The chemistry is aldehyde‐specific and exploits the inherent directionality of the chains in the cellulose I crystal bearing aldehyde groups exclusively on one end. This Review discusses challenges related to end‐specific modifications and highlights the opportunities for nanocellulose materials.

International audience; A new type of polysaccharide (hemicellulose) nanocrystal, bearing the shape of an anisotropic nanoflake, emerged from a dimethyl sulfoxide (DMSO) dispersion of wood-based xylan through heat-induced crystallization. The dimensions of these xylan nanocrystals were controlled by the crystallization conditions. Sharp signals in solid-state NMR indicated a well-ordered crystal structure. The unit cell is constituted of two asymmetric xylose residues, and DMSO molecules resided in a host–guest type of arrangement with more than one local environment. This corroborates with the identical 1H NMR relaxation time between DMSO and xylan, indicative of intimate mixing of the two at the tens of nanometer length scale. X-ray and electron diffraction indicated a 2-fold helical helix along the chain in a monoclinic unit cell with an antiparallel arrangement, with chains placed on the 2-fold helix axes: at the corner and at the center. The 2-fold helical structure is unique for xylan for which only a 3-fold helical form has been reported. The DMSO molecules participated in the crystallization, and they were shown to be vital in stabilizing the crystalline structure. The manipulation of temperature, concentration, and incubation time of the xylan/DMSO dispersion provided pathways for the crystallization to form size-adjustable nanocrystals. As 20–30% of biomass consists of hemicelluloses, this work will serve as a starting point to understand the controlled assembly of hemicelluloses to discover their full application potential.

An isolation method with mild mechanical agitation and no acidic extraction step from a mushroom substrate resulted in chitin nanofibers (ChNFs) with large shares of retained glucans (50-65%). The subsequent chitin nanopapers exhibited exceptionally high tensile strengths of >200 MPa and moduli of ca. 7 GPa, which were largely attributed to the preserved glucans in the mixture, imparting a composite nature to the nanopapers. The isolation method for ChNFs is notably different from the conventional process with crustacean chitin sources that do not incorporate glucans and where an acidic extraction step for the removal of minerals must always be included.

Cation transport through a cellulose acetate-poly(N,N-dimethylaminoethyl methacrylate) membrane (CA:PDMAEMA) was studied with scanning electrochemical microscope (SECM) and the thickness increase of the membrane was monitored with ellipsometry. Upon addition of the polyelectrolyte PDMAEMA, the permeability of the probe cation (ferrocenium methanol, FcMeOH) was increased as much as 40-fold. Soaking membranes in an electrolyte solution doubled the permeability in plain CA membranes, whereas for PDMAEMA containing membranes the opposite was observed and the permeability was reduced by 20–40%. This time-dependent behavior is shown to be a result of the presence of PDMAEMA within the membrane matrix, thus providing an interesting platform for controllable membrane permeability.

In an attempt to prepare cellulose nanocrystals (CNCs) by TEMPO-mediated oxidation of microcrystalline cellulose (MCC), a new species of MCC called AaltoCell was placed under scrutiny. Unlike Avicel, AaltoCell is a never-dried species, still containing ca. 10% xylan in its structure. According to thermoporosimetry, the pore size distributions of AaltoCell and Avicel did not differ from each other but after TEMPO-oxidation, AaltoCell exhibited a far lower degree of porosity, hypothetically ascribed to its hemicellulose content. Surprisingly, the charge density imposed by TEMPO-oxidation did not vary between AaltoCell and Avicel despite the different microfibril widths observed, respectively. After TEMPO-oxidation and centrifugation the fine fraction share, indicating the CNC yield, was not more than 11% for AaltoCell, compared to 20% from Avicel.

The rapid and uncontrollable corrosion of Mg and Mg based alloys is one of the main obstacles in the development of Mg based temporal implant materials1,2; the potentially harmful corrosion products leading to the increase of local pH and release of H2 gas to the surrounding tissues are especially problematic. Therefore, the control over the dissolution rate and release of corrosion products is of high importance if Mg based materials are to be used as temporary biomedical implants. Earlier, the authors have developed a weak polyelectrolyte-cellulose acetate membrane (poly(N,N-dimethylaminoethyl methacrylate)-cellulose acetate=PDMAEMA:CA membrane), which can simultaneously control the dissolution rate of Mg as well as protect the surrounding environment from the high pH increase and H2 gas3. In the present study, scanning electrochemical microscope (SECM) was used to investigate the transport properties of these membranes in more details. The results show that the PDMAEMA content controls the permeability of the membrane but also, a surprising time-dependent behaviour was observed: the permeability of the PDMAEMA:CA membranes decreased as a function of time and ellipsometer results showed that this behaviour is not related to the swelling of the membrane. Instead, the time-dependent behaviour might be an indicator of the conformational change of PDMAEMA molecules – either due to the screening of charges or change in degree of ionisation - blocking the membrane pores and this results in a change in permeability as a function of time. A material with such a time-dependent behaviour is an extremely interesting candidate when designing smart and responsive coatings and membranes for temporal biomedical implants. (1) F. Witte, N. Hort, C. Vogt, S. Cohen, K. U. Kainer, R. Willumeit, F. Feyerabend, Current Opinion in Solid State and Materials Science, 2008, 12, 63-72. (2) S. Virtanen, Mater. Sci. Eng. B, 2011, 176, 1600-1608. (3) K. Yliniemi, B. P. Wilson, F. Singer, S. Höhn, E. Kontturi S. Virtanen, ACS Applied Materials and Interfaces, 2014, 6, 22393-22399.

Biopolymer cellulose is investigated in terms of the crystallographic order within thin films. The films were prepared by spin-coating of a trimethylsilyl cellulose precursor followed by an exposure to HCl vapors; two different source materials were used. Careful precharacterization of the films was performed by infrared spectroscopy and atomic force microscopy. Subsequently, the films were investigated by grazing incidence X-ray diffraction using synchrotron radiation. The results showed broad diffraction peaks, indicating a rather short correlation length of the molecular packing in the range of a few nanometers. The analysis of the diffraction patterns was based on the known structures of crystalline cellulose, as the observed peak pattern was comparable to cellulose phase II and phase III. The dominant fraction of the film is formed by two different types of layers, which are oriented parallel to the substrate surface. The stacking of the layers results in a one-dimensional crystallographic order with a defined interlayer distance of either 7.3 or 4.2 A. As a consequence, two different preferred orientations of the polymer chains are observed. In both cases, polymer chain axes are aligned parallel to the substrate surface, and the orientation of the cellulose molecules are concluded to be either edge-on or flat-on. A minor fraction of the cellulose molecules form nanocrystals that are randomly distributed within the films. In this case, the molecular packing density was found to be smaller in comparison to the known crystalline phases of cellulose.

The structural component of fungal cell walls comprises of chitin covalently bonded to glucan; this constitutes a native composite material (chitin-glucan, CG) combining the strength of chitin and the toughness of glucan. It has a native nano-fibrous structure in contrast to nanocellulose, for which further nanofibrillation is required. Nanopapers can be manufactured from fungal chitin nanofibrils (FChNFs). FChNF nanopapers are potentially applicable in packaging films, composites, or membranes for water treatment due to their distinct surface properties inherited from the composition of chitin and glucan. Here, chitin-glucan nanofibrils were extracted from common mushroom (Agaricus bisporus) cell walls utilizing a mild isolation procedure to preserve the native quality of the chitin-glucan complex. These extracts were readily disintegrated into nanofibre dimensions by a low-energy mechanical blending, thus making the extract dispersion directly suitable for nanopaper preparation using a simple vacuum filtration process. Chitin-glucan nanopaper morphology, mechanical, chemical, and surface properties were studied and compared to chitin nanopapers of crustacean (Cancer pagurus) origin. It was found that fungal extract nanopapers had distinct physico-chemical surface properties, being more hydrophobic than crustacean chitin.

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.

A literature review on ultrathin films of cellulose is presented. The review focuses on different deposition methods of the films – all the way from simple monocomponent films to more elaborate multicomponent structures – and the use of the film structures in the vast realm of materials science. The common approach of utilizing cellulose thin films as experimental models is therefore omitted. The reader will find that modern usage of cellulose thin films constitutes an exciting emerging area within materials science and it goes far beyond the traditional usage of the films as model systems.

Cell therapy combined with biomaterial scaffolds is used to treat cartilage defects. We hypothesized that chondrogenic differentiation bone marrow-derived mesenchymal stem cells (BM-MSCs) in three-dimensional biomaterial scaffolds would initiate cartilaginous matrix deposition and prepare the construct for cartilage regeneration in situ. The chondrogenic capability of human BM-MSCs was first verified in a pellet culture. The BM-MSCs were then either seeded onto a composite scaffold rhCo-PLA combining polylactide and collagen type II (C2) or type III (C3), or commercial collagen type I/III membrane (CG). The BM-MSCs were either cultured in a proliferation medium or chondrogenic culture medium. Adult human chondrocytes (ACs) served as controls. After 3, 14, and 28 days, the constructs were analyzed with quantitative polymerase chain reaction and confocal microscopy and sulfated glycosaminoglycans (GAGs) were measured. The differentiated BM-MSCs entered a hypertrophic state by Day 14 of culture. The ACs showed dedifferentiation with no expression of chondrogenic genes and low amount of GAG. The CG membrane induced the highest expression levels of hypertrophic genes. The two different collagen types in composite scaffolds yielded similar results. Regardless of the biomaterial scaffold, culturing BM-MSCs in chondrogenic differentiation medium resulted in chondrocyte hypertrophy. Thus, caution for cell fate is required when designing cell-biomaterial constructs for cartilage regeneration.

Cerebral dopamine neurotrophic factor (CDNF) shows beneficial effects in rodent models of Parkinson’s and Alzheimer’s disease. The brain is a challenging target for protein therapy due to its exclusive blood–brain barrier. Hence, the therapeutic protein should be delivered directly to the brain parenchyma. Implantation of encapsulated mammalian cells that constantly secrete CDNF is a potential approach for targeted and long-term protein delivery to the brain. In this study, we generated several CDNF-secreting cell clones derived from human retinal pigment epithelial cell line ARPE-19, and studied CDNF secretion from the clones maintained as monolayers and in polymeric microcapsules. The secretion of wild type (wt) CDNF transgene was low and the majority of the produced protein remained intracellular, locating mainly to the endoplasmic reticulum (ER). The secretion of wtCDNF decreased to even lower levels when the clones were in a non-dividing state, as in the microcapsules. Both codon optimization and deletion of the putative ER-retrieval signal (four last amino acids: KTEL) improved CDNF secretion. More importantly, the secretion of KTEL-deleted CDNF remained constant in the non-dividing clones. Thus, cells expressing KTEL-deleted CDNF, in contrast to wtCDNF, can be considered for cell encapsulation applications if the KTEL-deleted CDNF is proven to be biologically active in vivo.

The goal of this study was to assess the sustainability of a modified cellulose nanofiber material for the recovery of precious gold from chloride solution, with a special focus on gold recovery from acidic solutions generated by cupric and ferric chloride leaching processes. TEMPO-oxidized cellulose nanofiber in hydrogel (TOCN), dry (H-TOCN, F-TOCN) and sheet form (S-TOCN) was examined for gold adsorptivity from chloride solution. Additionally, this work describes the optimum conditions and parameters for gold recovery. The data obtained in this investigation are also modeled using kinetic (pseudo first-order and pseudo second-order), isotherm best fit (Freundlich, Langmuir and Langmuir-Freundlich), and thermodynamic (endothermic process) parameters. Results demonstrate that high levels of gold removal can be achieved with TEMPO-oxidized cellulose nanofibers (98% by H-TOCNF) and the interaction characteristics of H-TOCN with gold suggests that other precious metals could also be efficiently recovered.

A novel approach to modifying native cellulosic fibres with poly(ethylene glycol) (PEG) impregnation and simultaneous cross-linking by citric acid (CA) was investigated. To understand the contributions of different components in the system, control references with just CA and cellulosic fibres (filter paper) were studied. The effect of sodium hypophosphite as a catalyst was also assessed. The results revealed that ester bonds are indeed formed in the cellulose–PEG–CA reaction system, as indicated by weight percentage gain (WPG) and FTIR analysis. The best results were achieved by using 5% CA and 10% PEG (calculated as weight-% from cellulose). In the reaction, the environmentally friendly CA prevents PEG from being leached out of cellulose during washing, resulting in promising future applications in dimensionally stabilized products based on cellulosic fibres.

Cellulose nanocrystal (CNC) production suffers, among other problems, from low yields. The focus of this study was to investigate the universal effect of charge density, centrifugation, and mechanical treatment as limiting causes of yield. Microcrystalline cellulose (MCC) was used as the starting material in order to eliminate the relatively arbitrary yield losses caused by the hydrolysis conditions. To disintegrate MCC into nanocrystals, high surface charge in the form of carboxylic groups was introduced by TEMPO-mediated oxidation, after which the material was mechanically treated, and separated into fine and coarse fractions. The fine fraction collected as supernatant after separation by centrifugation had a yield of 17–20% independent of the mechanical treatment method or time used. The particle sizes of these fractions did not significantly differ from each other, which raises questions on the efficiency of the mechanical treatment (sonication) and centrifugation in traditional CNC production. The results imply that radically new approaches in preparation are needed for truly meaningful increases in the CNC yield.

Utilizing a combination of atomic layer deposition and dip-coating techniques, we have incorporated natural nanocellulose fibers into an inorganic matrix in order to create a layered hybrid inorganic-organic thin-film structure. Such layer-engineered hybrid materials with an unorthodox combination of components are highly potential candidates for exciting new properties. Here, we show a more than an order of magnitude reduction in the cross-plane thermal conductivity for ZnO thin films achieved with the regular inclusion of the cellulose nanofiber layers. We foresee that a similar approach as presented here for ZnO could also be applied to other inorganic materials based on earth-abundant elements to influence their thermal transport properties.

The chalcone synthase superfamily consists of type III polyketidesynthases (PKSs), enzymes responsible for producing plant secondary metabolites with various biological and pharmacological activities. Anther-specific chalcone synthase-like enzymes (ASCLs) represent an ancient group of type III PKSs involved in the biosynthesis of sporopollenin, the main component of the exine layer of moss spores and mature pollen grains of seed plants. In the latter, ASCL proteins are localized in the tapetal cells of the anther where they participate in sporopollenin biosynthesis and exine formation within the locule. It is thought that the enzymes responsible for sporopollenin biosynthesis are highly conserved, and thus far, each angiosperm species with a genome sequenced has possessed two ASCL genes, which in Arabidopsis thaliana are PKSA and PKSB. The Gerbera hybrida (gerbera) PKS protein family consists of three chalcone synthases (GCHS1, GCHS3 and GCHS4) and three 2-pyrone synthases (G2PS1, G2PS2 and G2PS3). In previous studies we have demonstrated the functions of chalcone synthases in flavonoid biosynthesis, and the involvement of 2-pyrone synthases in the biosynthesis of antimicrobial compounds found in gerbera. In this study we expanded the gerbera PKS-family by functionally characterizing two gerbera ASCL proteins. In vitro enzymatic studies using purified recombinant proteins showed that both GASCL1 and GASCL2 were able to use medium and long-chain acyl-CoA starters and perform two to three condensation reactions of malonyl-CoA to produce tri- and tetraketide 2-pyrones, usually referred to as alpha-pyrones in sporopollenin literature. Both GASCL1 and GASCL2 genes were expressed only floral organs, with most expression observed in anthers. In the anthers, transcripts of both genes showed strict tapetum-specific localization. (C) 2016 Elsevier Ltd. All rights reserved.

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.

In light-activated liposomal drug delivery systems (DDSs), the light sensitivity can be obtained by a photothermal agent that converts light energy into heat. Excess heat increases the drug permeability of the lipid bilayer, and drug is released as a result. In this work, two near-IR responsive photothermal agents in a model drug delivery system are studied: either gold nanorods (GNRs) encapsulated inside the liposomes or indocyanine green (ICG) embedded into the lipid bilayer. The liposome system is exposed to light, and the heating effect is studied with fluorescent thermometers: laurdan and CdSe quantum dots (QDs). Both photothermal agents are shown to convert light into heat in an extent to cause a phase transition in the surrounding lipid bilayer. This phase transition is also proven with laurdan generalized polarization (GP). In addition to the heating results, we show that the model drug (calcein) is released from the liposomal cavity with both photothermal agents when the light power is sufficient to cause a phase transition in the lipid bilayer.

Native cellulose nanocrystals (CNCs) are valuable high quality materials with potential for many applications including the manufacture of high performance materials. In this work, a relatively effortless procedure was introduced for the production of CNCs, which gives a nearly 100% yield of crystalline cellulose. However, the processing of the native CNCs is hindered by the difficulty in dispersing them in water due to the absence of surface charges. To overcome these difficulties, we have developed a one-step procedure for dispersion and functionalization of CNCs with tailored cellulose binding proteins. The process is also applicable for polysaccharides. The tailored cellulose binding proteins are very efficient for the dispersion of CNCs due to the selective interaction with cellulose, and only small fraction of proteins (5-10 wt %, corresponds to about 3 μmol g(-1)) could stabilize the CNC suspension. Xyloglucan (XG) enhanced the CNC dispersion above a fraction of 10 wt %. For CNC suspension dispersed with carboxylmethyl cellulose (CMC) we observed the most long-lasting stability, up to 1 month. The cellulose binding proteins could not only enhance the dispersion of the CNCs, but also functionalize the surface. This we demonstrated by attaching gold nanoparticles (GNPs) to the proteins, thus, forming a monolayer of GNPs on the CNC surface. Cryo transmission electron microscopy (Cryo-TEM) imaging confirmed the attachment of the GNPs to CNC solution conditions.

Fungal chitin is attracting commercial and academic interest as a cheap, renewable, easily isolated and abundant alternative to crustacean chitin. Being covalently decorated with β-glucan, fungal chitin exhibits a native nanocomposite architecture that varies in fibre diameter and chitin to β-glucan ratio from species to species, resulting in mechanical properties ranging from brittle, high tensile strength, plastic-like properties to very tough and elastomeric rubber-like tensile properties if processed into paper form. This study utilised a mild alkaline process to extract chitin-β-glucan complexes from tree bracket fungi (D. confragosa) and common mushrooms (A. bisporus), which were then combined in varying ratios and hot pressed to form engineered composite nanopapers with tunable tensile properties. Fruiting bodies of common mushrooms, with almost proportional contents of chitin and β-glucan, exhibited a nanofibrous architecture resulting in very high tensile strengths, far outperforming crustacean-derived chitin. These nanopapers could then be plasticised in a controlled fashion through addition of extract from tree bracket fungi, which contains large quantities of β-glucan, to produce composite nanopapers. The fungal chitin extracts were significantly more hydrophobic than crustacean chitin, suggesting potential as a coating agent for hydrophilic materials, such as cellulose. These remarkable and controllable characteristics make fungi-derived materials versatile for a wide range of applications, including coatings, membranes, packaging and paper.

Despite their sustainable appeal, biomass components are currently undervalued in nanotechnology because means to control the assembly of bio-based nanoparticles are lagging behind the synthetic counterparts. Here, micrometer-sized particles consisting of aligned cellulose nanocrystals (CNCs) are prepared by crosslinking cellulose in cotton linter fibers that are prehydrolyzed with gaseous HCl, resulting in chemical cleavage necessary for CNC formation but retaining the morphology of the native fibers. That way, the intrinsic alignment of cellulose microfibrils within the fiber cell wall can be retained and utilized for top-down CNC alignment. Subsequent crosslinking with citric acid cements the alignment and preserves it, following the dispersion of CNCs trapped end-to-end, connected, and crosslinked within the colloidally stable micrometer-sized particles. Furthermore, thermoporosimetry and cryogenic transmission electron microscopy (Cryo TEM) shows that the particles possess mainly nanoporous (

The levelling-off degree of polymerization (LODP) is typically considered an apodictic number of each cellulosic source that relates to the length of its cellulose crystallites. In this study, we have performed hydrothermal and alkaline treatments on bleached birch kraft pulp to adjust the xylan content, and the resulting pulps have been subjected to acid hydrolysis to determine their LODP. The results show that hydrothermal treatments promote longitudinal alterations in the supramolecular structure of cellulose, represented by a linear decrease in the LODP with lowering the xylan content in the pulp. Moreover, a decrease in LODP is also observed after alkaline extraction of the birch kraft pulp, but the decrease as a function of xylan content differs from that observed after hydrothermal treatments. The results appear to indicate that the LODP is rather an artifact introduced during processing of the material than a true measure of the length of the crystallites in the native cellulose source. Graphical abstract: [Figure not available: see fulltext.].

openaire: EC/H2020/742829/EU//DRIVEN There is an emerging quest for lightweight materials with excellent mechanical properties and economic production, while still being sustainable and functionalizable. They could form the basis of the future bioeconomy for energy and material efficiency. Cellulose has long been recognized as an abundant polymer. Modified celluloses were, in fact, among the first polymers used in technical applications; however, they were later replaced by petroleum-based synthetic polymers. Currently, there is a resurgence of interest to utilize renewable resources, where cellulose is foreseen to make again a major impact, this time in the development of advanced materials. This is because of its availability and properties, as well as economic and sustainable production. Among cellulose-based structures, cellulose nanofibrils and nanocrystals display nanoscale lateral dimensions and lengths ranging from nanometers to micrometers. Their excellent mechanical properties are, in part, due to their crystalline assembly via hydrogen bonds. Owing to their abundant surface hydroxyl groups, they can be easily modified with nanoparticles, (bio)polymers, inorganics, or nanocarbons to form functional fibers, films, bulk matter, and porous aerogels and foams. Here, some of the recent progress in the development of advanced materials within this rapidly growing field is reviewed.

A cellulose degradation technique utilizing a pressurized HCl gas (up to 100 kPa) device is introduced. High pressure HCl quickly degraded cellulose in purified cotton linters, reaching the so-called levelling-off degree of polymerisation (LODP) in less than 1.5 h. LODP marks the point where the disordered portions of cellulose microfibrils have been degraded and only the crystalline portions remain, generally signalling the end of cellulose degradation unless remarkably high concentrations are used. In the present high pressure system, however, continued hydrolysis following the LODP was detected by incremental release of sugars from the hydrolysate after its exposure to water, supposedly caused by erosion from the cellulose crystallite ends. With minimal water consumption and the ease of recycling the gaseous acid, the technique could be a potential candidate for pre-treatment considering the future production of cellulose nanomaterials, particularly cellulose nanocrystals.

This research explores fundamental, structural differences of ultrathin films, prepared with three distinct deposition methods using 2,2,6,6-tetramethyl-piperidin-1-oxyl radical oxidized cellulose nanofibres (TEMPO-CNFs) derived from never dried bleached birch pulp. There is standard characterization by atomic force microscopy (morphology, roughness) and ellipsometry (thickness) and important structural data is gained by exposing the films to water vapor and monitoring the vapor uptake with quartz crystal microbalance (QCM). Significant distinctions were found from QCM data that could be linked to the structure of the films, originating from the three deposition methods: adsorption, spin coating and electrophoretic deposition. Moreover, the results shown here have potential implications for various types of films that comprise of amphiphilic nanomaterials that have a distinct response to moisture or aqueous based solutions.

International audience; Of the composite materials occurring in nature, the plant cell wall is among the most intricate, consisting of a complex arrangement of semicrystalline cellulose microfibrils in a dissipative matrix of lignin and hemicelluloses. Here, a biomimetic, two-dimensional cellulose system of the cell wall structure is introduced where cellulose nanocrystals compose the crystalline portion and regenerated amorphous cellulose composes the dissipative matrix. Spectroscopic ellipsometry and QCM-D are used to study the water vapor uptake of several two-layer systems. Quantitative analysis shows that the vapor-induced swelling of these ultrathin films can be controlled by varying ratios of the chemically identical ordered and unordered cellulose components. Intriguingly, increasing the share of crystalline cellulose appeared to increase the vapor uptake but only in cases for which the interfacial area between the crystalline and amorphous area was relatively large and the thickness of an amorphous overlayer was relatively small. The results show that a biomimetic approach may occasionally provide answers as to why certain native structures exist.

International audience; Despite the structural, load-bearing role of cellulose in the plant kingdom, countless efforts have been devoted to degrading this recalcitrant polysaccharide, particularly in the context of biofuels and renewable nanomaterials. Herein, we show how the exposure of plant-based fibers to HCl vapor results in rapid degradation with simultaneous crystallization. Because of the unchanged sample texture and the lack of mass transfer out of the substrate in the gas/solid system, the changes in the crystallinity could be reliably monitored. Furthermore, we describe the preparation of cellulose nanocrystals in high yields and with minimal water consumption. The study serves as a starting point for the solid-state tuning of the supramolecular properties of morphologically heterogeneous biological materials.

This letter proposes a strategy to construct tunable films combining the physical characteristics of cellulose nanofibrils and smart polymers for membrane applications. A functional membrane template was obtained by first fabricating a water stable film from cellulose nanofibrils and subsequently surface grafting it with a thermoresponsive polymer, poly(N-isopropylacrylamide). The behavior of the membrane template was dependent on temperature. The increment in slope of relative water permeance around the lower critical solution temperature of poly(N-isopropylacrylamide) increased from 18 to 100% upon polymer attachment. Although the membrane template essentially consisted of wood-based materials, the benefits of smart synthetic polymers were achieved.