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Cellulose is an appealing material for tissue engineering. In an attempt to overcome some obstacles with cellulose II cell scaffolding materials related to insufficient biomineralization, lack of micron-size porosity, and deficiency in surface charge, respective solutions have been proposed. These included covalent phosphorylation of different cellulose materials targeting relatively low degrees of substitution (DS 0.18-0.23) and processing these cellulose derivatives into scaffolding materials by a dissolution/coagulation approach employing the hitherto rarely used TBAF/DMSO/H 2 O system for cellulose dissolution. Here, we report bioactivity and preliminary hemocompatibility testing of dual-porous cellulose phosphate aerogels (contrasted with the phosphate-free reference) obtained via coagulation (water/ethanol), solvent exchange and scCO 2 drying. Deposition of hydroxyapatite from simulated body fluid (7 days of immersion) revealed good bioactivity (1.5-2.2 mg Ca 2+ per mg scaffold). Incubation of the scCO 2 -dried and rehydrated scaffolding materials in heparin anticoagulated human whole blood was conducted to study selected parameters of hemostasis (prothrombin F1+2 fragment, PF4, count of thrombocyte-leukocyte conjugates) and inflammatory response (C5a fragment, leukocyte activation marker CD11b). Adhesion of leukocytes on the surface of the incubated substrates was assessed by scanning electron and fluorescence microscopy (DAPI staining). The results suggest that phosphorylation at low DS does not increase platelet activation. However, a significant increase in platelet activation and thrombin formation was observed after a certain fraction of the negative surface charges had been compensated by Ca 2+ ions. The combination of both phosphorylation and calcification turned out to be a potent means for controlling the inflammatory response, which was close to baseline level for some of the studied samples., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Schimper, Pachschwöll, Maitz, Werner, Rosenau and Liebner.)

Mesenchymal stem cells (MSCs) are the most prominent type of adult stem cells for clinical applications. Three-dimensional (3D) cultivation of MSCs in biomimetic hydrogels provides a more physiologically relevant cultivation microenvironment for in vitro testing and modeling, thus overcoming the limitations of traditional planar cultivation methods. Cellulose nanofibers are an excellent candidate biomaterial for synthesis of hydrogels for this application, due to their biocompatibility, tunable properties, availability, and low cost. Herein, we demonstrate the capacity of hydrogels prepared from 2,2,6,6-tetramethylpiperidine-1-oxyl -oxidized and subsequently individualized cellulose-nanofibrils to support physiologically relevant 3D in vitro cultivation of human MSCs at low solid contents (0.2-0.5 wt %). Our results show that MSCs can spread, proliferate, and migrate inside the cellulose hydrogels, while the metabolic activity and proliferative capacity of the cells as well as their morphological characteristics benefit more in the lower bulk cellulose concentration hydrogels.

All -lignin coating formulations were prepared while combining water-soluble cationic kraft lignin (quaternized LignoBoost ® , CL) and anionic lignosulphonate (LS). The electrostatic attraction between positively charged CL and negatively charged LS led to the formation of insoluble self-organized macromolecule aggregates that align to films. The structures of the formed layers were evaluated by atomic force microscopy (AFM), firstly on glass lamina using dip-coating deposition and then on handsheets and industrial uncoated paper using roll-to-roll coating in a layer-by-layer mode. Coated samples were also characterized by optical microscopy, scanning electron microscopy (SEM) coupled with energy dispersive spectroscopy (SEM/EDS), and contact angle measurements. It was suggested that the structure of all -lignin aggregates is the result of the interaction of amphiphilic water-soluble lignin molecules leading to their specifically ordered mutual arrangement depending on the order and the mode of their application on the surface. The all -lignin coating of cellulosic fiber imparts lower air permeability and lower free surface energy to paper, mainly due to a decrease in surface polarity, thus promoting the paper's hydrophobic properties. Moderate loading of lignin coating formulations (5-6 g m -2 ) did not affect the mechanical strength of the paper.

Current changes toward a more biobased economy have recently created tremendous renewed interest in using lignin as a valuable source for chemicals and materials. Here, we present a facile cationization approach aiming to impart kraft lignin water-solubility, with similar good features as lignosulfonates. Eucalyptus globulus kraft lignin obtained from a paper mill black liquor by applying the LignoBoost process was used as the substrate. Its reaction with 3-chloro-2-hydroxypropyl-trimethylammonium chloride (CHPTAC) in an aqueous alkaline medium was studied to assess the impact of different reaction conditions (temperature, time, educt concentration, molar CHPTAC-to-lignin ratio) on the degree of cationization. It has been shown that at pH 13, 10 wt % lignin content, 70 °C, and 3 h reaction time, a CHPTAC-to-lignin minimum molar ratio of 1.3 is required to obtain fully water-soluble products. Elemental analysis (4.2% N), size-exclusion chromatography ( M w 2180 Da), and quantitative 13 C NMR spectroscopy of the product obtained at this limit reactant concentration suggest introduction of 1.2 quaternary ammonium groups per C9 unit and substitution of 75% of the initially available phenolic OH groups. The possible contribution of benzylic hydroxyls to the introduction of quaternary ammonium moieties through a quinone methide mechanism has been proposed. Since both molecular characteristics and degree of substitution, and hence solubility or count of surface charge, of colloidal particles can be adjusted within a wide range, cationic kraft lignins are promising materials for a wide range of applications, as exemplarily demonstrated for flocculation of anionic dyes., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

This study investigates the effect of the enzymatic polymerization of lignosulfonate for the formulation of a lignosulfonate-based adhesive. For this, beech lamellas were glued together and tested according to the EN 302-1 standard. The results showed that the laccase-polymerized lignosulfonate-based wood adhesives (LS-p) had similar mechanical properties as a standard carpenter's glue (PVAc-based D3 class white glue), as no significant difference in tensile shear strength between these two adhesive types was found. However, carpenter's glue showed almost 100% wood failure, while with the lignosulfonate-based wood glue, the samples failed, mainly in the glueline. Pre-polymerization of LS-p is the most critical factor to achieve the required viscosity, which is also connected to the wetting properties and the resulting tensile shear strength. The longer the pre-polymerization, the higher the viscosity of the LS-p adhesive, with the tensile shear strength reaching a plateau. The presented data show the potential of using enzymatically pre-polymerized lignosulfonate as a well-performing wood adhesive. Further development and optimization of the pre-polymerization process is required, which is also important to push towards upscaling and practical applications.

Coating of steel is a frequently applied approach to increase the resistance of moving machine parts towards abrasion, surface oxidation, and corrosion. Here, we show that plating circular saw blades with certain metals can help to reduce the electrical charging of wood dust during cutting, which has significant implications for occupational safety, healthcare, and lifetime of filter systems. With the example of beech wood planks, machine net energy consumption E V (J cm -3 ) and cumulated field strength E→V (kV m -4 ) as caused by electrically charged particles were compared for cutting of 10- and 20-mm deep grooves (800 mm length) using saw blades of different toothing (24, 60 teeth) and surface coating (Cu, Ag, and Cr). To ensure uniform feed per tooth ( f z = 0.063 mm), saw blades were operated at different rotation speeds (4000 vs. 1600 rpm). The results demonstrate that the extent of electrostatic sawdust charging can be manipulated to a certain extent by the type of saw blade plating. Coating with chromium turned out to be most effective in shifting the electrostatic charge of the wood particles towards neutralization. Lowering of rotation speed using circular saw blades of higher toothing was an additional measure significantly reducing electrostatic charging of wood dust. Hence, cutting with a chrome-coated blade with 60 teeth can be specifically recommended as the reduction of electrical saw dust charging is not associated with higher machine power consumption.

The imaging of non-conducting materials by scanning electron microscopy (SEM) is most often performed after depositing few nanometers thick conductive layers on the samples. It is shown in this work, that even a 5 nm thick sputtered gold layer can dramatically alter the morphology and the surface structure of many different types of aerogels. Silica, polyimide, polyamide, calcium-alginate and cellulose aerogels were imaged in their pristine forms and after gold sputtering utilizing low voltage scanning electron microscopy (LVSEM) in order to reduce charging effects. The morphological features seen in the SEM images of the pristine samples are in excellent agreement with the structural parameters of the aerogels measured by nitrogen adsorption-desorption porosimetry. In contrast, the morphologies of the sputter coated samples are significantly distorted and feature nanostructured gold. These findings point out that extra care should be taken in order to ensure that gold sputtering does not cause morphological artifacts. Otherwise, the application of low voltage scanning electron microscopy even yields high resolution images of pristine non-conducting aerogels.

According to the International Energy Agency, biorefinery is "the sustainable processing of biomass into a spectrum of marketable bio-based products (chemicals, materials) and bioenergy (fuels, power, heat)". In this review, we survey how the biorefinery approach can be applied to highly porous and nanostructured materials, namely aerogels. Historically, aerogels were first developed using inorganic matter. Subsequently, synthetic polymers were also employed. At the beginning of the 21st century, new aerogels were created based on biomass. Which sources of biomass can be used to make aerogels and how? This review answers these questions, paying special attention to bio-aerogels' environmental and biomedical applications. The article is a result of fruitful exchanges in the frame of the European project COST Action "CA 18125 AERoGELS: Advanced Engineering and Research of aeroGels for Environment and Life Sciences".

Biopolymer aerogels of appropriate open-porous morphology, nanotopology, surface chemistry, and mechanical properties can be promising cell scaffolding materials. Here, we report a facile approach towards the preparation of cellulose phosphate aerogels from two types of cellulosic source materials. Since high degrees of phosphorylation would afford water-soluble products inappropriate for cell scaffolding, products of low DS P (ca. 0.2) were prepared by a heterogeneous approach. Aiming at both i) full preservation of chemical integrity of cellulose during dissolution and ii) utilization of specific phase separation mechanisms upon coagulation of cellulose, TBAF·H 2 O/DMSO was employed as a non-derivatizing solvent. Sequential dissolution of cellulose phosphates, casting, coagulation, solvent exchange, and scCO 2 drying afforded lightweight, nano-porous aerogels. Compared to their non-derivatized counterparts, cellulose phosphate aerogels are less sensitive towards shrinking during solvent exchange. This is presumably due to electrostatic repulsion and translates into faster scCO 2 drying. The low DS P values have no negative impact on pore size distribution, specific surface ( S BET ≤ 310 m 2 g -1 ), porosity (Π 95.5-97 vol.%), or stiffness ( E ρ ≤ 211 MPa cm 3 g -1 ). Considering the sterilization capabilities of scCO 2 , existing templating opportunities to afford dual-porous scaffolds and the good hemocompatibility of phosphorylated cellulose, TBAF·H 2 O/DMSO can be regarded a promising solvent system for the manufacture of cell scaffolding materials.

Bacterial cellulose (BC) features a nanofibrillar network structure that can provide a good template for quantum dots (QDs), to overcome the fluorescence quenching-effect of QDs in polymer composites. Here, we fabricated novel fluorescent aerogels with tunable emission by covalently binding environmentally-friendly ZnS(CuInS 2 )/ZnS core-shell quantum dots along the nanofibrillar BC. A new ligand of 3-(mercaptopropyl)trimethoxysilane allows QDs to transfer from toluene to alcohol solvent and stably bind to the BC. After supercritical CO 2 drying, the resulting BC-QDs aerogels maintain the porous nanofibrillar morphology of BC with ultra-light-weight, the QDs are well-distributed along the BC fiber surfaces without aggregation. The emission wavelength can be tuned in a wide range from 470 to 750 nm by simply adjusting the QDs core component or shell layers. This work provides a new approach for fabricating QDs-polymer hydrogels and aerogels with well distributed QDs via chemical binding that potential as smart sensor, catalysis, and 3D display applications., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Zinc-copper-indium sulfide (ZCIS)-alloyed quantum dots are emerging as a new family of low toxic I-III-VI semiconductors due to their broad and color-tunable emissions as well as large Stokes shifts. Here, we fabricated a series of ZCIS QDs with tunable PL wavelengths and band-gap energies via a facile strategy by varying the ratio of A1-3 stock (Cu + /In 3+ ) to the B stock (Zn 2+ ) content. The ZnS shell was formed to improve the PL emission efficiency of the core nanoparticles and the PL emission wavelength of the resulting ZCIS/ZnS NCs gradually blue-shifted with an increase in the number of shell layers, resulting in a wide range of emissions from 800 nm to 518 nm that can be tuned by the core compositions or shell layer numbers for ZCIS/ZnS. Finally, the long-chain ligands dodecanethiol/octadecylamine on the quantum dots' surface were efficiently replaced by (3-mercaptopropyl)trimethoxysilane, thus enabling their solubility in an ionic liquid, which was confirmed via GC-MS. It also benefited for the co-dissolution of the polymers and chemical binding with other materials through the reactive silanol group, which provide stable and well-distributed ZCIS/ZnS QDs composites or surface coating by the QDs., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Aerogels are a special class of nanostructured materials with very high porosity and tunable physicochemical properties. Although a few types of aerogels have already reached the market in construction materials, textiles and aerospace engineering, the full potential of aerogels is still to be assessed for other technology sectors. Based on current efforts to address the material supply chain by a circular economy approach and longevity as well as quality of life with biotechnological methods, environmental and life science applications are two emerging market opportunities where the use of aerogels needs to be further explored and evaluated in a multidisciplinary approach. In this opinion paper, the relevance of the topic is put into context and the corresponding current research efforts on aerogel technology are outlined. Furthermore, key challenges to be solved in order to create materials by design, reproducible process technology and society-centered solutions specifically for the two abovementioned technology sectors are analyzed. Overall, advances in aerogel technology can yield innovative and integrated solutions for environmental and life sciences which in turn can help improve both the welfare of population and to move towards cleaner and smarter supply chain solutions., Competing Interests: The authors declare no conflict of interest.

The growing incidence of chronic wounds in the world population has prompted increased interest in chronic wound dressings with protease-modulating activity and protease point of care sensors to treat and enable monitoring of elevated protease-based wound pathology. However, the overall design features needed for the combination of a chronic wound dressing that lowers protease activity along with protease detection capability as a single platform for semi-occlusive dressings has scarcely been addressed. The interface of dressing and sensor specific properties (porosity, permeability, moisture uptake properties, specific surface area, surface charge, and detection) relative to sensor bioactivity and protease sequestrant performance is explored here. Measurement of the material's zeta potential demonstrated a correlation between negative charge and the ability of materials to bind positively charged Human Neutrophil Elastase. Peptide-cellulose conjugates as protease substrates prepared on a nanocellulosic aerogel were assessed for their compatibility with chronic wound dressing design. The porosity, wettability and absorption capacity of the nanocellulosic aerogel were consistent with values observed for semi-occlusive chronic wound dressing designs. The relationship of properties that effect dressing functionality and performance as well as impact sensor sensitivity are discussed in the context of the enzyme kinetics. The sensor sensitivity of the aerogel-based sensor is contrasted with current clinical studies on elastase. Taken together, comparative analysis of the influence of molecular features on the physical properties of three forms of cellulosic transducer surfaces provides a meaningful assessment of the interface compatibility of cellulose-based sensors and corresponding protease sequestrant materials for potential use in chronic wound sensor/dressing design platforms.

Nanocellulose has high specific surface area, hydration properties, and ease of derivatization to prepare protease sensors. A Human Neutrophil Elastase sensor designed with a nanocellulose aerogel transducer surface derived from cotton is compared with cotton filter paper, and nanocrystalline cellulose versions of the sensor. X-ray crystallography was employed along with Michaelis-Menten enzyme kinetics, and circular dichroism to contrast the structure/function relations of the peptide-cellulose conjugate conformation to enzyme/substrate binding and turnover rates. The nanocellulosic aerogel was found to have a cellulose II structure. The spatiotemporal relation of crystallite surface to peptide-cellulose conformation is discussed in light of observed enzyme kinetics. A higher substrate binding affinity ( K m ) of elastase was observed with the nanocellulose aerogel and nanocrystalline peptide-cellulose conjugates than with the solution-based elastase substrate. An increased K m observed for the nanocellulosic aerogel sensor yields a higher enzyme efficiency ( k cat / K m ), attributable to binding of the serine protease to the negatively charged cellulose surface. The effect of crystallite size and β-turn peptide conformation are related to the peptide-cellulose kinetics. Models demonstrating the orientation of cellulose to peptide O6-hydroxymethyl rotamers of the conjugates at the surface of the cellulose crystal suggest the relative accessibility of the peptide-cellulose conjugates for enzyme active site binding., Competing Interests: The authors declare no conflict of interest.

Interfacing nanocellulosic-based biosensors with chronic wound dressings for protease point of care diagnostics combines functional material properties of high specific surface area, appropriate surface charge, and hydrophilicity with biocompatibility to the wound environment. Combining a protease sensor with a dressing is consistent with the concept of an intelligent dressing, which has been a goal of wound-dressing design for more than a quarter century. We present here biosensors with a nanocellulosic transducer surface (nanocrystals, nanocellulose composites, and nanocellulosic aerogels) immobilized with a fluorescent elastase tripeptide or tetrapeptide biomolecule, which has selectivity and affinity for human neutrophil elastase present in chronic wound fluid. The specific surface area of the materials correlates with a greater loading of the elastase peptide substrate. Nitrogen adsorption and mercury intrusion studies revealed gas permeable systems with different porosities (28-98%) and pore sizes (2-50 nm, 210 µm) respectively, which influence water vapor transmission rates. A correlation between zeta potential values and the degree of protease sequestration imply that the greater the negative surface charge of the nanomaterials, the greater the sequestration of positively charged neutrophil proteases. The biosensors gave detection sensitivities of 0.015-0.13 units/ml, which are at detectable human neutrophil elastase levels present in chronic wound fluid. Thus, the physical and interactive biochemical properties of the nano-based biosensors are suitable for interfacing with protease sequestrant prototype wound dressings. A discussion of the relevance of protease sensors and cellulose nanomaterials to current chronic wound dressing design and technology is included.

We present an approach to construct biocompatible and photoluminescent hybrid materials comprised of carbon quantum dots (CQDs) and TEMPO-oxidized cellulose nanocrystals (TO-CNCs). First, the amino-functionalized carbon quantum dots (NH 2 -CQDs) were synthesized using a simple microwave method, and the TO-CNCs were prepared by hydrochloric acid (HCl) hydrolysis followed by TEMPO-mediated oxidation. The conjugation of NH 2 -CQDs and TO-CNCs was conducted via carbodiimide-assisted coupling chemistry. The synthesized TO-CNC@CQD hybrid nanomaterials were characterized using X-ray photoelectron spectroscopy, cryo-transmittance electron microscopy, confocal microscopy, and fluorescence spectroscopy. Finally, the interactions of TO-CNC@CQD hybrids with HeLa and RAW 264.7 macrophage cells were investigated in vitro. Cell viability tests suggest the surface conjugation with NH 2 -CQDs not only improved the cytocompatibility of TO-CNCs, but also enhanced their cellular association and internalization on both HeLa and RAW 264.7 cells after 4 and 24 h incubation.

Ammoxidation of pine kraft lignin in aqueous 5 wt % ammonia affords a novel type of phenol substitute that significantly accelerates resole synthesis and curing as demonstrated for 40 wt % phenol replacement. Compared to non-ammoxidized lignin, which already shortens significantly the cooking time required to reach a resole viscosity of 1000 Pa·s (250 vs. 150 s) and reduces the typical curing B-time by about 25% at 100 °C, the use of ammoxidized lignin has an even more pronounced impact in this respect. Activation of lignin by Fenton-type oxidation prior to ammoxidation further boosts both synthesis and curing of the resole. This is presumably due to the intermediary formation of polyvalent cross-linkers like N,N,N-tris (methylol) trimethylene triamine triggered by saponification of a larger fraction of nitrogenous moieties present in such a treated lignin (ammonium salts, amide-type nitrogen, urea) and reaction of the released ammonia with formaldehyde. Except for the fact that phenol replacement by ammoxidized lignin results in a somewhat less brittle cured adhesive polymer and higher elastic modulus, the aforementioned acceleration in curing could no longer be observed in the presence of wood, where a significantly delayed wood-adhesive bond formation was observed for the lignin-containing adhesives as evident from the automated bonding evaluation system.

Nanocellulosic aerogels (NA) provide a lightweight biocompatible material with structural properties, like interconnected high porosity and specific surface area, suitable for biosensor design. We report here the preparation, characterization and activity of peptide-nanocellulose aerogels (PepNA) made from unprocessed cotton and designed with protease detection activity. Low-density cellulosic aerogels were prepared from greige cotton by employing calcium thiocyanate octahydrate/lithium chloride as a direct cellulose dissolving medium. Subsequent casting, coagulation, solvent exchange and supercritical carbon dioxide drying afforded homogeneous cellulose II aerogels of fibrous morphology. The cotton-based aerogel had a porosity of 99% largely dominated by mesopores (2-50 nm) and an internal surface of 163 m²·g -1 . A fluorescent tripeptide-substrate (succinyl-alanine-proline-alanine-4-amino-7-methyl-coumarin) was tethered to NA by (1) esterification of cellulose C6 surface hydroxyl groups with glycidyl-fluorenylmethyloxycarbonyl (FMOC), (2) deprotection and (3) coupling of the immobilized glycine with the tripeptide. Characterization of the NA and PepNA included techniques, such as elemental analysis, mass spectral analysis, attenuated total reflectance infrared imaging, nitrogen adsorption, scanning electron microscopy and bioactivity studies. The degree of substitution of the peptide analog attached to the anhydroglucose units of PepNA was 0.015. The findings from mass spectral analysis and attenuated total reflectance infrared imaging indicated that the peptide substrate was immobilized on to the surface of the NA. Nitrogen adsorption revealed a high specific surface area and a highly porous system, which supports the open porous structure observed from scanning electron microscopy images. Bioactivity studies of PepNA revealed a detection sensitivity of 0.13 units/milliliter for human neutrophil elastase, a diagnostic biomarker for inflammatory diseases. The physical properties of the aerogel are suitable for interfacing with an intelligent protease sequestrant wound dressing., Competing Interests: The authors declare no conflicts of interest.