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Carbohydrate-binding modules (CBM) have emerged as useful tools for a wide range of tasks, including the use as purification tags or for cellulose fiber modification. For this purpose, the CBM needs to be attached to a target protein leading to large constructs. We investigated if short peptides from the carbohydrate binding site of CBMs can bind in a similar way as native, full-length CBMs to nanocrystalline cellulose (NCC) or cotton linter paper. We designed our cellulose-binding peptides to be less hydrophobic and shorter than those previously reported. Starting from the binding site of Cel7A-CBM1, we incorporated the essential amino acids involved in cellulose binding into our peptides. These peptides, as well as control peptides with scrambled sequences or a lack of essential amino acids, bound to cellulose with similar affinity as CBM regardless of their secondary structure, sequence, or hydrophobicity. This unspecific mode of cellulose binding displayed by the presented peptides may be exploited to functionalize cellulose-based biomaterials by means of peptide-conjugates.

Despite the potential of lignocellulose in manufacturing value-added chemicals and biofuels, its efficient biotechnological conversion by enzymatic hydrolysis still poses major challenges. The complex interplay between xylan, cellulose, and lignin in fibrous materials makes it difficult to assess underlying physico- and biochemical mechanisms. Here, we reduce the complexity of the system by creating matrices of cellulose, xylan, and lignin, which consists of a cellulose base layer and xylan/lignin domains. We follow enzymatic degradation using an endoxylanase by high-speed atomic force microscopy and surface plasmon resonance spectroscopy to obtain morphological and kinetic data. Fastest reaction kinetics were observed at low lignin contents, which were related to the different swelling capacities of xylan. We demonstrate that the complex processes taking place at the interfaces of lignin and xylan in the presence of enzymes can be monitored in real time, providing a future platform for observing phenomena relevant to fiber-based systems.

This study conducted a detailed evaluation of the feasibility of producing cellulose microfibrils (CMF) from a kraft-bleached hardwood pulp at high solid contents with and without pretreatments. CMFs produced by planetary ball milling at solid contents 17 and 28% were compared with those from 1 to 5% under the same milling conditions. Fiber pretreatments using a commercial endoglucanase and mechanical refining using a laboratory PFI mill were also applied before ball milling at a solid content of 28%. Two mechanisms of fiber fibrillation were identified from the results obtained: (i) ball and fiber/fibril interactions─the primary mechanism and (ii) interfiber/fibril frictional and tensional interactions─the secondary mechanism. The secondary mechanism plays an important role only in early-stage fibrillation and became less important as fibrillation proceeded in the later stage toward nanofibrillation. Improving fiber dispersion at lower solid content facilitated fibrillation. Endoglucanase pretreatment substantially shortened fibers to result in a "pulverized-like" CMF with short fibrils at an extended milling time. Mechanical refining of fibers facilitated fibrillation to result in CMFs with a morphology similar to that from runs without any fiber pretreatment but for a much shorter milling time. Both CMF water retention value (WRV) measurements and CMF suspension sedimentation experiments showed results consistent with imaging observations. The insights gained through this study provide relevant information with commercial significance regarding CMF production at high solids, which is not currently available in the literature.

β-Cyclodextrin (β-CD) is often used as a drug carrier for biomedical materials due to its unique cavity structure. Herein, β-CD was modified by acryloyl chloride and further copolymerized with N -isopropylacrylamide (NIPAM) and acrylic acid (AA) to obtain PNIPAM -co- β-CD-AC. The results showed that the critical phase transition temperature of PNIPAM/β-CD-AC could be controlled at 19 °C, and the fast sol-gel phase transition was realized in 2-10 s. The hydrophobic drug carried in this hydrogel can constantly be released for more than 6 days at pH values (pH 5.5-8), and the duration may match the recovery of the wound. As a dressing hydrogel, its rapid gel formation and inversion as well as shear-thinning behavior prevent secondary wound damage. The β-CD-based hydrogel also has good biocompatibility and antioxidant properties, which provide a good potential choice for wound dressings, especially for exposed wounds in winter.

Nanocomposites have been widely used in many important areas due to their particular physical/chemical properties; however, just though a simple technology, endowing multiple functions into a single nanomaterial for realizing their multifunctional applications is still a challenge. Here, we report a robust method for the facile synthesis of Ag-based multifunctional nanocomposites via using tannin-coated phenol-formaldehyde resin nanospheres (TA-PFRN) as silver nanoparticle (Ag NP) carriers. The thickness of the tannin coating is readily tuned from 50 to 320 nm by regulating the concentration of tannin added. Under the optimal conditions, the TA-PFRN has a 23.8 wt % of Ag NPs loading capacity with only 17.2 nm Ag NP layers. Consequently, the novel TA-PFRN@Ag nanocomposites possess multiple functions and integrated characteristics. As catalysts, the catalytic efficiency of TA-PFRN@Ag is nearly 6 times higher than that of the PFRN@Ag. As highly effective free radical initiators, TA-PFRN@Ag nanocomposites can trigger ultrafast acrylic acid (AA)/acrylamide (AM) polymerization at room temperature (in only a few minutes). As nano-reinforced fillers, the addition of 0.04 wt % nanocomposites can improve the tensile strength of PVA film from 60 to 153.2 MPa. In addition, the nanocomposites can also serve as antibacterial agents, efficiently inhibiting the growth of Escherichia coli ( E. coli ) and Staphylococcus aureus ( S. aureus ); as antiultraviolet agents, the presence of TA-PFRN@Ag nanocomposites endows the film/hydrogel materials excellent ultraviolet (UV) shielding. This work provides a novel strategy for the green synthesis of Ag-based multifunctional nanocomposites that show promising applications in catalysis, nanomaterials, and biomedicine.

The engineering of a new type of trifunctional biopolymer-based nanosponges polymerized by cross-linking beta-cyclodextrin ethylene diamine (βCD-EDA) with bifunctional hairy nanocellulose (BHNC) is reported herein. We refer to the highly cross-linked polymerized BHNC-βCD-EDA network as BBE. βCD-EDA and BHNC were cross-linked at various ratios with the help of DMTMM (4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium) as a green activator in deionized water as a solvent, which resulted in different morphological shapes of BBE. Some of these structures were chiral due to cross-linked liquid crystalline structures. A comprehensive characterization study was done to show their unique morphological, structural, and dimensional properties of BBEs. Moreover, to further investigate and to confirm the surface modification of the precursors and final BBE structures, Fourier transform infrared and nuclear magnetic resonance spectroscopy, thermogravimetric analysis, Brunauer-Emmett-Teller analysis, and X-ray diffraction were applied. The hairy nanocellulose particles were considered as the backbone, and the immobilized cyclodextrin cavities can capture doxorubicin, which was used as a model drug molecule via host-guest inclusion complexation. Finally, the obtained BBE networks showed different and sustained drug release profiles and pH responsiveness. BBE biopolymers were tested as biocompatible nanocarriers for controlled release. We realize that these structures are too big for anti-cancer drug delivery by injection or oral intake, but these structures have a high potential to be applied in wound dressing and implants. They could also be used for capturing antibiotics, dyes, and organic compounds from wastewater.

With the rapid increase of diabetes cases in the world, there is an increasing demand for slowing down and managing diabetes and its effects. It is considered that a viable prophylactic treatment for type 2 diabetes mellitus (T2DM) is to reduce carbohydrate digestibility by controlling the activities of α-amylase and α-glucosidase to control postprandial hyperglycemia and promote the growth of intestinal beneficial bacteria. In this work, the effects of sulfonated lignin with different sulfonation degrees (0.8 mmol/g, SL 1 ; 2.9 mmol/g, SL 2 ) on the inhibition of α-amylase and α-glucosidase and the proliferation of intestinal beneficial bacteria in vitro were investigated. The results showed that both SL 1 and SL 2 can inhibit the activity of α-amylase and α-glucosidase. The inhibition capacity (IC 50 , 32.35 μg/mL) of SL 2 with a low concentration (0-0.5 mg/mL) to α-amylase was close to that of acarbose to α-amylase (IC 50 , 27.33 μg/mL). Compared with the control groups, the bacterial cell concentrations of Bifidobacteria adolescentis and Lactobacillus acidophilus cultured with SL 1 and SL 2 increased in varying degrees (8-36%), and the produced short-chain fatty acids were about 1.2 times higher. This work demonstrates the prospect of sulfonated lignin as a prebiotic for the prevention and treatment of T2DM, which provides new insights for opening up a brand new field of lignin.

Here, we describe the all-aqueous bicontinuous emulsions with cholesteric liquid crystal domains through hierarchical colloidal self-assembly of nanoparticles. This is achieved by homogenization of a rod-like cellulose nanocrystal (CNC) with two immiscible, phase separating polyethylene glycol (PEG) and dextran polymer solutions. The dispersed CNCs exhibit unequal affinity for the binary polymer mixtures that depends on the balance of osmotic and chemical potential between the two phases. Once at the critical concentration, CNC particles are constrained within one component of the polymer phases and self-assemble into a cholesteric organization. The obtained liquid crystal emulsion demonstrates a confined three-dimensional percolating bicontinuous network with cholesteric self-assembly of CNC within the PEG phase; meanwhile, the nanoparticles in the dextran phase remain isotropic instead. Our results provide an alternative way to arrest bicontinuous structures through intraphase trapping and assembling of nanoparticles, which is a viable and flexible route to extend for a wide range of colloidal systems.

The fabrication of commercial cellulose nanofibrils (CNFs) into arrays with long-range ordering is of great significance for their extended applications, which, however, is severely hindered by their high disorder, aggregation, and hornified features. Herein, sub-nanoscale anionic metal oxide clusters (phosphotungstic acid, H 3 PW 12 O 40 , PTA) are applied to complex with commercial CNFs (dried powder DCNF and aqueous suspension WCNF) in aqueous media, and a long-range ordered layer structure can be facilely fabricated via typical unidirectional freezing. The surface complexation of the commercial CNFs and PTA can be confirmed through the small-angle scattering studies of the complex hydrogels. The hydrogels present similar correlation lengths in small-angle X-ray and neutron scattering measurements, suggesting the homogeneous distribution of PTA along the commercial CNFs. This gives rise to the negatively charged surface feature and further leads to strong repulsion among the commercial CNFs. Due to the disparity in sizes, the influence of PTA on the density of hydrogel networks is suppressed, and the network density is mainly dependent on the mass content of CNFs. The studies provide guidance to fabricate hydrogels with catalytic and photosensitive properties and also to design and stabilize long-range ordered structured aerogels during the removal of the nonfreezing bound water absorbed by the commercial CNFs after unidirectional freezing. This facile strategy shows great potential to broaden the application of commercial CNFs in thermal insulators, super-adsorbent materials, and supercapacitors in electrical devices.

Cellulose nanocrystals (CNCs) offer excellent mechanical properties. However, measuring the strength by performing reliable experiments at the nanoscale is challenging. In this paper, we model Iβ crystalline cellulose using reactive molecular dynamics simulations. Taking the fibril twist into account, structural changes and hydrogen-bonding characteristics of CNCs during the tensile test are inspected and the failure mechanism of CNCs is analyzed down to the scale of individual bonds. The C4-O4 glycosidic bond is found to be responsible for the failure of CNCs. Finally, the effect of strain rate on ultimate properties is analyzed and a nonlinear model is used to predict the ultimate strength of 9.2 GPa and ultimate strain of 8.5% at a 1 s -1 strain rate. This study sheds light on the applications of cellulose in nanocomposites and further modeling of cellulose nanofibres.

Cellulose nanopaper is an attractive film material exhibiting huge potential in various fields, while its terrible water stability greatly hinders practical applications. Previous efforts on addressing this issue usually sacrifice the sustainability or material performance of film. In this study, we report a high-performing lignocellulosic nanopaper with superior water resistance and excellent optical properties. The strategy involves preparing a lignin-containing cellulose nanopaper (LCNP) first, and then infiltrating metal ions into the film to build cross-linking interactions within the fiber networks. Owing to the coordination bonds formed between metal ions and lignocellulosic components, the resulting metal ions cross-linked LCNP (M + -LCNP) displays outstanding water resistance, including the highest wet mechanical strength of ∼52 MPa after immersing in water for 24 h, which retains nearly 47% of the dry mechanical strength of the film. The ultralow water uptake ratio of ∼35% also confirms it possesses a superior wet dimensional stability. Moreover, these nanopapers also showcase the desired optical performances, including both high visible transmittance (>85%) and total ultraviolet-blocking efficiency (>91%, only transmitting a little of UVA). Overall, this fully degradable film is a promising alternative to replacing conventional plastics that are applied in multiple areas.

The gradually depleting fossil resources and the biosafety of bisphenol A have always restricted the green development of the traditional epoxy resin field. In this Article, biomass macromolecule lignin sulfonates are selected as the raw material instead of traditional bisphenol A to prepare lignin-based epoxy resin adhesives. Lignin sulfonates are chemically modified and combined with a cross-linking agent to form lignin-based epoxy resin adhesives with double-interpenetrating-network structures. The resulting lignin-based epoxy adhesive exhibits a maximum tensile shear strength of 11.29 MPa, which is 213% higher than the strength before chemical modification. The tensile shear strength of the adhesive is still 10.13 MPa after 12 h of immersion in water (20 °C), and its tensile shear strength is 9.30 MPa after 12 h of immersion in boiling water (100 °C). The high-temperature and high-humidity environment has no significant effect on the properties of the resulting lignin-based epoxy adhesive.

As a natural antitumor drug, curcumin (CUR) has received increasing attention from researchers and patients due to its various medicinal properties. However, currently CUR is still restricted due to its low and stand-alone therapeutic effects that seriously limit its clinical application. Here, by using cellulose nanocrystals (CNCs) as a nanocarrier to load CUR and AuNPs simultaneously, we developed a hybrid nanoparticle as a codrug delivery system to enhance the low and stand-alone therapeutic effects of CUR. Aided with the encapsulation of β-cyclodextrin (βCD), both the solubility and the stability of CUR are greatly enhanced (solubility increased from 0.89 to 131.7 μg/mL). Owing to the unique rod-like morphology of CNCs, the system exhibits an outstanding loading capacity of 31.4 μg/mg. Under the heat effects of coloaded AuNPs, the system demonstrates a high release rate of 77.63%. Finally, with CNC as a bridge nanocarrier, all aforementioned functions were integrated into one hybrid nanoparticle. The all-in-one integration ensures CUR to have enhanced therapeutic effects and enables the delivery system to exhibit combined chemo-photothermal therapy outcomes. This work presents a significant step toward CUR's clinical application and provides a new strategy for effective and integrative treatment of tumor disease.

Cellulose nanocrystals (CNC) are green, safe, and renewable nanomaterials with a variety of excellent performances but their morphologies are notoriously difficult to control as this is unfavorable to the diversification of the end products. Allomorphic conversion plays an important role in diversifying the morphology of CNC. However, this further complicates the prediction, design, and control of the geometric dimensions of CNC. Herein, allomorphically modified cellulose (mercerized cellulose, ethylenediamine (EDA)-treated cellulose, and ball-milled cellulose) is designed and used as the starting material for CNC isolation. Subsequently, the morphological evolution of cellulose particles during acid hydrolysis is traced by scanning electron microscopy observations. A mechanism that facilitates further understanding of CNC shaping during sulfuric acid hydrolysis is proposed. According to the CNC shaping mechanism, precise prediction, design, and efficient control of the morphology of CNC (needle-like, ribbon-like, ellipsoid, and spherical) can be realized. CNC with various morphologies are favorable for their applications, such as templating synthesis of porous materials and Pickering emulsion dispersion.

Cellulose-water interactions are crucial to understand biological processes as well as to develop tailor made cellulose-based products. However, the main challenge to study these interactions is the diversity of natural cellulose fibers and alterations in their supramolecular structure. Here, we study the humidity response of different, well-defined, ultrathin cellulose films as a function of industrially relevant treatments using different techniques. As treatments, drying at elevated temperature, swelling, and swelling followed by drying at elevated temperatures were chosen. The cellulose films were prepared by spin coating a soluble cellulose derivative, trimethylsilyl cellulose, onto solid substrates followed by conversion to cellulose by HCl vapor. For the highest investigated humidity levels (97%), the layer thickness increased by ca. 40% corresponding to the incorporation of 3.6 molecules of water per anhydroglucose unit (AGU), independent of the cellulose source used. The aforementioned treatments affected this ratio significantly with drying being the most notable procedure (2.0 and 2.6 molecules per AGU). The alterations were investigated in real time with X-ray reflectivity and quartz crystal microbalance with dissipation, equipped with a humidity module to obtain information about changes in the thickness, roughness, and electron density of the films and qualitatively confirmed using grazing incidence small angle X-ray scattering measurements using synchrotron irradiation.

Thehighly efficient utilization of lignin is of great importance for the development of the biorefinery industry. Herein, a novel "core-shell" lignin nanoparticle (LNP) with a diameter of around 135 nm was prepared, after the lignin was isolated from the effluent of formic acid fractionation via dialysis. In an attempt to endow composite materials with vital functionalities, the LNP was added to the starch film and the starch/polyvinyl alcohol (PVA) or starch/polyethylene oxide (PEO) composite film. The results showed that the hydrophobicity performance of the synthesized films was enhanced significantly. Specifically, the dynamic water contact angle value of the starch/PVA composite film with 1% (wt) addition of LNPs could be maintained as high as 122° for 180 s; the starch/PEO composite film also achieved an excellent water contact angle above 120°. The addition of LNPs promoted the formation of some rough structures on the film surface, as shown by the scanning electron microscopy images, which could repel the water molecules efficiently and are closely related to the enhanced hydrophobicity of the starch film. What is more, the as-prepared LNP conferred strengthened thermal stability and ultraviolet blocking properties on the starch composite film. The structural combination of the polymer film with LNPs holds the promise for providing advanced functionalities to the composite material with wide applications.

Bioactive substances, displaying excellent biocompatibility, chemical stability, and processability, could be extensively applied in biomedicine and tissue engineering. In recent years, plant-based bioactive substances such as flavonoids, vitamins, terpenes, and lignin have received considerable attention due to their human health benefits and pharmaceutical/medical applications. Among them is lignin, an amorphous biomacromolecule mainly derived from the combinatorial radical coupling of three phenylpropane units ( p -hydroxypenyl, guaiacyl, and syringyl) during lignification. Lignin possesses intrinsic bioactivities (antioxidative, antibacterial, anti-UV activities, etc.) against phytopathogens. Lignin also enhances the plant resistance (adaptability) against environmental stresses. The abundant structural features of lignin offer other significant bioactivities including antitumor and antivirus bioactivities, regulation of plant growth, and enzymatic hydrolysis of cellulose. This Review reports the latest research results on the bioactive potential of lignin and lignin-based substances in biomedicine, agriculture, and biomass conversion. Moreover, the interfacial reactions and bonding mechanisms of lignin with biotissue/cells and other constituents were also discussed, aiming at promoting the conversion or evolution of lignin from industrial wastes to value-added bioactive materials.

The fabrication of biomimetic photonic materials with environmental stimuli-responsive functions from entirely biobased materials is becoming increasingly challenging with the growing demand for biodegradable materials. Herein, the effect of glucan with different molecular weights on the mechanical performance and tunable structural color of iridescent CNC composite films was investigated. The existence of glucan did not influence the self-assembly performance of CNCs, but rather led to an improvement in the mechanical performance, enabling cholesteric CNC composite films with an adjustable structural color. Simultaneously, the iridescent films showed a conspicuous redshift and enlarged initial pitch without obstruction of the chiral structure. In response to environmental humidity, the structural colors of the iridescent composite films can be changed by regulating their chiral nematic structure. In particular, the films demonstrate a reversible structural color change between blue and red at RH between 50 and 98%. The resulting biobased iridescent composite films have potential applications in decorative coating, optical and humidity sensing, and anticounterfeiting.

Xylan-based films have great potential to replace petroleum-based polymers used for packaging and coatings due to their excellent biocompatibility, biodegradability, and good gas barrier properties. However, fabricating a xylan-based film with flexible, transparent, water-proof, and excellent mechanical properties is an enormous challenge. Herein, we manufactured a series of degradable films with adjustable properties via solution-casting using a water-soluble xylan derivative. This is the first report of a pure xylan-based film with high performance, requiring no additives. The tensile strength of the xylan-based film could be controlled by adjusting the aldehyde content, which varied from 105.0 to 132.6 MPa. The smallest initial water contact angle of the xylan-based films is 93.26°, indicating that these films are hydrophobic. This work shows a simple and viable route toward manufacturing xylan-based films with high tensile strength, flexibility, and transparency, which can be used for packaging materials and coatings.

Lignin/tannin/ZnONP composite coatings were designed for paper-based green packaging. Multiple functions, such as high strength, moisture resistance, low air permeance, heat endurance, UV aging resistance, and antibacterial/mold properties, were successfully integrated into one biobased coating. Prepolymerization improved the physical properties of coatings at high lignin contents. The best ingredient ratio was: 40% lignin, 15% tannin, and 10% ZnONPs (based on tannin weight), and the as-prepared biocoating was labeled LTZn-10. After coated with LTZn-10, the tensile strength and bursting strength of the packaging were efficiently enhanced by more than 3 times and were dramatically increased by 51.6 and 5.6 times at the wet state, respectively, which reveals that the packaging has favorable moisture resistance and it can be used in high humidity environments. Scanning electron microscopy (SEM) proved that most of the pores on the paper were blocked by the coatings, which helped to decrease the air permeance by 10.3 times. Meanwhile, ZnONPs were evenly spread on the coatings, which endowed the packaging with excellent antibacterial/mold performance. No colony or mycelium was found in the test against Gram-negative/positive bacteria and eight common molds. Besides, antibacterial activity is only available while the bacteria come in contact with the coating and no active substances were released into the culture medium, which is a good property that can keep the cargo from contamination of antibacterial agents. In addition, the coated paper presented an improved T and thermal degradation temperature, indicating that the coated package has favorable thermostability and can maintain its outstanding physical properties in a wider temperature range. Lignin and tannin promoted the UV stability and service life of the coated paper, as a rare physical decrease was observed after UV aging for 72 h. The function-integrated biobased coating with favorable sustainability is a good candidate to be widely used in paper-based green packaging fields.g and thermal degradation temperature, indicating that the coated package has favorable thermostability and can maintain its outstanding physical properties in a wider temperature range. Lignin and tannin promoted the UV stability and service life of the coated paper, as a rare physical decrease was observed after UV aging for 72 h. The function-integrated biobased coating with favorable sustainability is a good candidate to be widely used in paper-based green packaging fields.

Herein, we report a novel two-step method for the covalent, site-directed, and efficient immobilization of proteins on lab-made paper sheets. First, paper fibers were modified with a peptidic anchor comprising enzyme recognition motifs. Four different conjugation strategies for peptide immobilization were evaluated with respect to reproducibility and fiber loading efficiency. After manufacturing of the peptide-preconditioned paper, oriented conjugation of the model protein tGFP containing a C-terminal recognition sequence for either sortase A or microbial transglutaminase was assessed semiquantitatively by fluorescence measurement and inspected by confocal laser scanning microscopy (CLSM). The two enzymes utilized for protein conjugation used the same oligoglycine peptide anchor, and both proved to be suitable for controlled oriented linkage of substrate proteins at physiological conditions.

Efficiently preparing a starch-based plastic with moisture insensitivity and toughness is a challenge to improve the high-value utilization of polysaccharide resources. Herein, a sustainable, recyclable starch-based plastic was prepared in a facile and eco-friendly way. First, starch acetoacetate (SAA) with different degrees of substitution (DSs) was synthesized by transesterification. Then, the SAA film was obtained through a solvent-free hot-pressing method. Notably, SAA with different DSs exhibited various glass transition temperatures (109-140 °C), and SAA with high DS (>0.84) was insoluble even after boiling in water for 1 h. Also, the maximum fracture strength of SAA film up to 15.5 MPa and a maximum elongation at break up to 30% were reached . In addition, the starch-based plastic film retained the original mechanical properties after three cycles of hot processing. In consideration of the facile preparation process, this protocol provided a new avenue for developing sustainable and recyclable starch-based plastics.

Efficient enzymatic hydrolysis of cellulose in lignocellulose to glucose is one of the most critical steps for the production of biofuels. The nonproductive adsorption of lignin to expensive cellulase highly impedes the development of biorefinery. Understanding the lignin-cellulase interaction mechanism serves as a vital basis for reducing such nonproductive adsorption in their practical applications. Yet, limited report is available on the direct characterization of the lignin-cellulase interactions. Herein, for the first time, the nanomechanics of the biomacromolecules including lignin, cellulase, and cellulose were systematically investigated by using a surface force apparatus (SFA) at the nanoscale in aqueous solutions. Interestingly, a cation-π interaction was discovered and demonstrated between lignin and cellulase molecules through SFA measurements with the addition of different cations (Na + , K + , etc.). The complementary adsorption tests and theoretical calculations further confirmed the validity of the force measurement results. This finding further inspired the investigation of the interaction between lignin and other noncatalytic-hydrolysis protein (i.e., soy protein). Soy protein was demonstrated as an effective, biocompatible, and inexpensive lignin-blocker based on the molecular force measurements through the combined effects of electrostatic, cation-π, and hydrophobic interactions, which significantly improved the enzymatic hydrolysis efficiencies of cellulose in pretreated lignocellulosic substrates. Our results offer quantitative information on the fundamental understanding of the lignin-cellulase interaction mechanism. Such unraveled nanomechanics provides new insights into the development of advanced biotechnologies for addressing the nonproductive adsorption of lignin to cellulase, with great implications on improving the economics of lignocellulosic biorefinery.

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 increase in crystallinity index as the hydrolysis proceeded. The results provide a modern visual complement to >100 years of research in cellulose degradation.

Cellulose nanofibrils, which attract extensive attention as a bio-based, sustainable, high-performance nanofibril, are believed to be predominantly hydrophilic. This study aimed to prove the presence of an amphiphilic "Janus-type fiber surface" in water with hydrophobic and hydrophilic faces in a cellulose nanofibril (ACC-CNF) that was prepared by the aqueous counter collision method. We clarified the surface characteristics of the ACC-CNF by confocal laser scanning microscopy with a carbohydrate-binding module and congo red probes for the hydrophobic planes on the cellulose fiber surfaces and calcofluor white as hydrophilic plane probes. The results indicated the presence of both characteristic planes on a single ACC-CNF surface, which verifies an amphiphilic Janus-type structure. Both hydrophobic probes adsorbed onto ACC-CNFs for the quantitative evaluation of the degree of ACC-CNF surface hydrophobicity by Langmuir's adsorption theory based on the optimal maximum adsorption amounts for various starting raw material types.

The rheological behavior of aqueous suspensions of lignocellulose nanofibrils (LCNFs) is investigated systematically by considering the coupled effect of residual lignin and LCNF morphology. The LCNF was obtained by high-energy fluidization of TEMPO-oxidized mechanical fibers, followed by size fractionation (fibril widths of ∼5, ∼9, and ∼18 nm). The nanofibril width and the corresponding fibril-fibril interactions are strongly influenced by the presence and distribution of lignin in the respective fractions, either retained on the fibril surface or as free structures present in the finest size fraction. All samples containing lignin display dilatancy, typifying gel suspensions with aggregated hydrophobic particles. Fine fractionated samples display strong gel behavior. The coarse fractionated sample, by contrast, shows a greater tendency to flocculate via entanglement and displays less gel-like characteristics; hence, it dewaters more freely.

UV filters that contain one or two aromatic rings in conventional sunscreens generally have a poor photo- and thermal stability and can easily penetrate through stratum corneum and dermis into the blood vessel, thus causing potential health-threatening issues. Herein, a series of bioinspired photostable and biocompatible polydopamine-grafted lignin (AL-PDA) with strong bioadhesion have been synthesized through free radical addition of dopamine (DA) and alkali lignin (AL). AL-PDA was used to emulsify organic UV filters and further cross-linked to form nanocapsules through ultrasonic cavitation. The retention rate of optimal AL-PDA nanocapsules on the skin surface reached 87% after a thorough rinse with water and negligible penetration was observed, which demonstrates their excellent bioadhesion property. Force measurements using atomic force microscopy (AFM) quantitatively revealed the adhesion between the nanocapsules and skin. An average DA grafting number of 4 would be required to endow the AL-PDA nanocapsules with suitable water-penetration resistance. The nanocapsules were used as the sole active ingredient for formulating sunscreen, whose sun protection factor (SPF) value could reach 195.33 with a dosage ∼10 wt % lasting for over 8 h under UV radiation. The as-prepared nanocapsules possess excellent antioxidant capacity and biocompatibility, ensuring their superior performance and safe use in the sunscreen. This work provides new insights into the development of biomass lignin for advanced function materials and high-end products.

Here we investigate the relationship between thermomechanical properties and chemical structure of well-characterized lignin-based epoxy resins. For this purpose, technical lignins from eucalyptus and spruce, obtained from the Kraft process, were used. The choice of lignins was based on the expected differences in molecular structure. The lignins were then refined by solvent fractionation, and three fractions with comparable molecular weights were selected to reduce effects of molar mass on the properties of the final thermoset resins. Consequently, any differences in thermomechanical properties are expected to correlate with molecular structure differences between the lignins. Oxirane moieties were selectively introduced to the refined fractions, and the resulting lignin epoxides were subsequently cross-linked with two commercially available polyether diamines (Mn = 2000 and 400) to obtain lignin-based epoxy resins. Molecular-scale characterization of the refined lignins and their derivatives were performed by 31 P NMR, 2D-NMR, and DSC methods to obtain the detailed chemical structure of original and derivatized lignins. The thermosets were studied by DSC, DMA, and tensile tests and demonstrated diverse thermomechanical properties attributed to structural components in lignin and selected amine cross-linker. An epoxy resin with a lignin content of 66% showed a Tg of 79 °C from DMA, Young's modulus of 1.7 GPa, tensile strength of 66 MPa, and strain to failure of 8%. The effect of molecular lignin structure on thermomechanical properties was analyzed, finding significant differences between the rigid guaiacyl units in spruce lignin compared with sinapyl units in eucalyptus lignin. The methodology points toward rational design of molecularly tailored lignin-based thermosets.

To improve the salt tolerance/sensitivity of cellulose nanofibrils (CNFs), zwitterionic cellulose nanofibrils (ZCNFs) were prepared from softwood bleached kraft pulp fibers via a sequential process of anionic modification with 2,2,6,6-tetramethylepiperidin-1-oxyl (TEMPO)-mediated oxidation, cationic modification with (2,3-epoxypropyl) trimethylammonium chloride (EPTMAC), and high-pressure homogenization. To produce ZCNFs with different contents of cation group, EPTMAC loadings of 0.15 to 1.15 g/g fiber were explored during cationization. The obtained ZCNFs were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectra (XPS), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), and rheological measurements. The salt tolerance of the ZCNFs was investigated by adding mixed salts into the ZCNF dispersions. The results demonstrated that the ZCNFs with both anionic and cationic charges were produced. Compared with the TEMPO-mediated oxidized cellulose nanofibrils (TOCNFs), the ZCNFs exhibited an excellent "salt-thickening" behavior under the studied salt concentrations (2-24% w/w). Moreover, increasing the content of the cation group increased the salt tolerance/sensitivity of ZCNFs. This work demonstrated that introducing cationic charges to the anionic charged TOCNFs imparts the produced ZCNFs with excellent salt sensitivity and tolerance, which could expand the application of nanocellulose in oil recovery or wastewater treatment.

Biodegradable and renewable materials, such as cellulose nanomaterials, have been studied as a replacement material for traditional plastics in the biomedical field. Furthermore, in chronic wound care, modern wound dressings, hydrogels, and active synthetic extracellular matrices promoting tissue regeneration are developed to guide cell growth and differentiation. Cells are guided not only by chemical cues but also through their interaction with the surrounding substrate and its physicochemical properties. Hence, the current work investigated plant-based cellulose nanomaterials and their surface characteristic effects on human dermal fibroblast (HDF) behavior. Four thin cellulose nanomaterial-based coatings produced from microfibrillar cellulose (MFC), cellulose nanocrystals (CNC), and two TEMPO-oxidized cellulose nanofibers (CNF) with different total surface charge were characterized, and HDF viability and adhesion were evaluated. The highest viability and most stable adhesion were on the anionic CNF coating with a surface charge of 1.14 mmol/g. On MFC and CNC coated surfaces, HDFs sedimented but were unable to anchor to the substrate, leading to low viability.

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 Å. 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.

Stretchable and compressible hydrogels based on natural polymers have received immense considerations for electronics. The feasibility of using pure natural polymer-based hydrogels could be improved if their mechanical behaviors satisfy the requirements of practical applications. Herein, we report highly stretchable (tensile strain ∼126%) and compressible (compression strain ∼80%) cellulose ionic hydrogels (CIHs) among pure natural polymer-based hydrogels including cellulose, chitin, and chitosan via chemical cross-linking based on free radical polymerization of allyl cellulose in NaOH/urea aqueous solution. In addition, the hydrogels have good transparency (transmittance of ∼89% at 550 nm) and ionic conductivity (∼0.16 mS cm -1 ) and can be worked at -20 °C without freezing and visual loss of transparency. Moreover, the CIHs can serve as reliable and stable strain sensors and have been successfully used to monitor human activities. Significantly, the various properties of hydrogel can be controlled through rationally adjusting the chemically cross-linked density. Our methodology will prove useful in developing the satisfied mechanical and transparent CIHs for a myriad of applications in flexible electronics.

The molecular solubility of softwood arabinoglucuronoxylan (AGX) has been thoroughly investigated, and it has been shown that the chemical and physical structures of the extracted hemicellulose are not significantly influenced by different purification steps, but a transient molecular solubility of AGX was observed in aqueous media at low concentrations (1 g/L) when the dissolved macromolecules had a hydrodynamic diameter of up to 10 nm. A phase separation was detected when the concentration was increased to 15 g/L leading to an association of the smaller molecules into fractal structures with a considerably larger diameter, even though the dispersions were still transparent to ocular inspection. Dynamic Light Scattering and Cryo-Transmission Electron Microscopy showed dimensions in the range of 1000 nm. The phase separation of the sample was further characterized by estimating the χ-interaction parameter of AGX in water using the Flory-Huggins theory, and the results supported that water is a poor solvent for AGX. This behavior is crucial when films and hydrogels based on these biopolymers are made, since the association will dramatically affect barrier and mechanical properties of films made from these materials.

Nanotechnology has been identified as having great potential for improving the efficiency of water prevention and purification while reducing costs. In this field, two applications of nanocellulose have generated attention and have proven to be a sound strategy as an adsorbent and as a membrane for the removal of contaminants. This potential is attributed to its high aspect ratio, high specific surface area, high capacity retention, and environmental inertness. In addition to the aforementioned advantages, the presence of active sites allows the incorporation of chemical moieties that may enhance the binding efficiency of pollutants to the surface. This review paper intends to understand how nanocellulose affects the adsorption behavior of water pollutants, e.g., heavy metal ions, microbes, dyes, and organic molecules, and is divided in two parts. First, a general overview of the different strategies for the preparation of nanocellulose is described, and its specific properties are reported. The second section reports some of its application as adsorbent nanomaterial or separation membrane. It appears that the use of nanocellulose for these applications is very promising for wastewater treatment industries.

The three-dimensional (3D) printed scaffolds were prepared by partial cross-linking of TEMPO-oxidized cellulose nanofibril/alginate hydrogel using calcium ions for printing the hydrogel while maintaining its shape, fidelity, and preventing the collapse of the filaments. The prepared scaffolds were fully cross-linked using calcium ions immediately after printing to provide the rigidity of the hydrogel and give it long-term stability. The composition of the prepared pastes was adjusted in view of the description of the hydrogel and 3D printing parameters. The rheological properties in terms of thixotropic behavior and viscosity recovery of hydrogels were investigated by performing steady shear rate experiments. The results show that the viscosity recovery for pure alginate hydrogel was only about 16% of the initial value, whereas it was 66% when adding cellulose nanofibrils to alginate. Consequently, the shape of the pure alginate scaffold was soft and easy to collapse contrarily to the composite scaffold. The biomimetic mineralization process of printed scaffolds using simulated body fluid, mimicking the inorganic composition of human blood plasma, was performed and the hydroxyapatite nucleation on the hydrogel was confirmed. The strength properties of the fabricated scaffolds in terms of compressive strength analysis were also investigated and discussed. The results show that the alginate/TEMPO-oxidized cellulose nanofibril system may be a promising 3D printing scaffold for bone tissue engineering.

It is demonstrated that the molecular solubility of softwood hemicelluloses is significantly influenced by pretreatment of the fibers, extraction, and downstream processing. To quantify these effects, four hemicellulose samples were extracted from different thermomechanical pulps of Norway spruce. The molecular solubility of the samples was characterized by size and molar mass distributions, and the morphology of the molecules was studied using high resolution microscopy techniques. All extracted samples were well dispersed in aqueous media creating transparent dispersions, but dynamic light scattering measurements showed that molecular solubility can only be achieved using specific pretreatments and extractions. The procedure yields acetylated galactoglucomannan (AcGGM)-rich hemicelluloses with an average molar mass of 21-35 kDa and a diameter up to 10 nm but also shows that water is a poor solvent for this sample since an association is detected as soon as the concentration is about 20 g/L. These associated hemicellulose dispersions are still absolutely clear on visual inspection, underlining the need for careful measurement when assessing the solubility of wood hemicelluloses.

Knowledge gaps in the biosafety data of the nanocellulose (NC) for biomedical use through various routes of administration call for closer look at health and exposure evaluation. This work evaluated the potentially immunogenic contaminants levels, for example, endotoxin and (1,3)-β-d-glucan, in four representative NCs, that is, wood-based NCs and bacterial cellulose (BC). The hot-water extracts were analyzed with ELISA assays, HPSEC-MALLS, GC, and NMR analysis. Varying levels of endotoxin and (1,3)-β-d-glucan contaminats were found in these widely used NCs. Although the β-(1,3)-d-glucan was not detected from the NMR spectra due to the small extract samples amount (2-7 mg), the anomerics and highly diastereotopic 6-CH 2 signals may suggest the presence of β-(1,4)-linkages with β-(1,6) branching in the polysaccharides of NCs' hot-water extracts, which were otherwise not detectable in the enzymatic assay. In all, the article highlights the importance of monitoring various water-soluble potentially immunogenic contaminants in NC for biomedical use.

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.

The state of dispersion and the interactions between a polymer and a filler in a nanocomposite crucially define its properties and performance. The affinity of polylactide (PLA) with vegetable and animal proteins (casein, gelatin, soy protein isolate, and hydrolysate) is investigated and their role as eco-friendly dispersants and compatibilizers of cellulose nanofibrils (CNF) is elucidated. The affinity of the proteins with PLA is determined by using sensograms acquired by electroacoustic (quartz crystal microgravimetry) and optical (surface plasmon resonance) techniques. The surface energy of PLA increases upon protein adsorption while the opposite effect is observed for CNF, under identical experimental conditions. A significant improvement in the thermodynamic work of adhesion for PLA/CNF systems is predicted by application of the denatured proteins at low concentrations (∼20% and ∼15% enhancement with soy protein and casein at pH 3 and pH 8, respectively). We offer a robust method to screen denatured proteins and to tailor the wettability and material compatibility in the synthesis of bionanocomposites based on CNF and PLA.

The current study aims to demonstrate the influence of the surface chemistry of wood-derived cellulose nanofibril (CNF) hydrogels on fibroblasts for tissue engineering applications. TEMPO-mediated oxidation or carboxymethylation pretreatments were employed to produce hydrogels with different surface chemistry. This study demonstrates the following: first, the gelation of CNF with cell culture medium and formation of stable hydrogels with improved rheological properties; second, the response of mouse fibroblasts cultured on the surface of the hydrogels or sandwiched within the materials with respect to cytotoxicity, cell attachment, proliferation, morphology, and migration. Indirect cytotoxicity tests showed no toxic effect of either hydrogel. The direct contact with the carboxymethylated hydrogel adversely influenced the morphology of the cells and limited their spreading, while typical morphology and spreading of cells were observed with the TEMPO-oxidized hydrogel. The porous fibrous structure may be a key to cell proliferation and migration in the hydrogels.

We present an efficient approach to develop cellulose nanocrystal (CNC) hybrids with magnetically responsive Fe 3 O 4 nanoparticles that were synthesized using the (Fe 3+ /Fe 2+ ) coprecipitation. After 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-catalyzed oxidation of CNC, carbodiimide (EDC/NHS) was used for coupling amine-containing iron oxide nanoparticles that were achieved by dopamine ligand exchange (NH 2 -Fe 3 O 4 NPs). The as-prepared hybrids (Fe 3 O 4 @CNC) were further complexed with Cu(II) ions to produce specific protein binding sites. The performance of magnetically responsive Cu-Fe 3 O 4 @CNC hybrids was assessed by selectively separating lysozyme from aqueous media. The hybrid system displayed a remarkable binding capacity with lysozyme of 860.6 ± 14.6 mg/g while near full protein recovery (∼98%) was achieved by simple elution. Moreover, the regeneration of Fe 3 O 4 @CNC hybrids and efficient reutilization for protein separation was demonstrated. Finally, lysozyme separation from matrices containing egg white was achieved, thus revealing the specificity and potential of the presented method.

The temperature-dependence of xyloglucan (XG) adsorption onto smooth cellulose model films regenerated from N-methylmorpholine N-oxide (NMMO) was investigated using surface plasmon resonance spectroscopy, and it was found that the adsorbed amount increased with increasing temperature. This implies that the adsorption of XG to NMMO-regenerated cellulose is endothermic and supports the hypothesis that the adsorption of XG onto cellulose is an entropy-driven process. We suggest that XG adsorption is mainly driven by the release of water molecules from the highly hydrated cellulose surfaces and from the XG molecules, rather than through hydrogen bonding and van der Waals forces as previously suggested. To test this hypothesis, the adsorption of XG onto cellulose was studied using cellulose films with different morphologies prepared from cellulose nanocrystals (CNC), semicrystalline NMMO-regenerated cellulose, and amorphous cellulose regenerated from lithium chloride/dimethylacetamide. The total amount of high molecular weight xyloglucan (XGHMW) adsorbed was studied by quartz crystal microbalance and reflectometry measurements, and it was found that the adsorption was greatest on the amorphous cellulose followed by the CNC and NMMO-regenerated cellulose films. There was a significant correlation between the cellulose dry film thickness and the adsorbed XG amount, indicating that XG penetrated into the films. There was also a correlation between the swelling of the films and the adsorbed amounts and conformation of XG, which further strengthened the conclusion that the water content and the subsequent release of the water upon adsorption are important components of the adsorption process.

Cellulose nanofibrils (CNFs) are produced and commonly used in the form of aqueous suspensions or gels. A number of studies have focused lately on rheological properties of CNF suspensions, which gives insight into properties of such materials and can reflect their behavior during handling. This Review summarizes the recent progress in rheological studies on CNF aqueous suspensions using rotational rheometry. Here, we discuss linear viscoelastic properties, i.e., frequency-dependent storage and loss moduli; shear flow behavior, i.e., apparent viscosity and shear stress as a function of shear rate; local flow characteristics, etc. In this Review, we point out that the rheological behavior of at least two types of CNF suspensions should be distinguished: (i) ones produced using mechanical fibrillation with or without enzymatic pretreatment (no surface chemical modification), which possess highly flocculated structure, and (ii) ones produced involving chemical modification pretreatments, e.g., carboxylation, carboxymethylation, quaternization, or sulfonation, which possess better colloidal stability and do not evidently flocculate.

Lignins are complex and heterogeneous natural polymers in which the major units are characterized by certain prominent interunit linkages. Previous attempts to identify and quantify 4-O-5-linked units in softwood lignins by NMR were not successful. In this work, various lignin model compounds, including the tetramers formed by the 4-O-5-coupling of β-O-4-, β-β-, and β-5-model dimers, were synthesized. Such compounds are better able to model the corresponding structures in lignins than those used previously. 4-O-5-Linked structures could be clearly observed and identified in real softwood lignin samples by comparison of their 2D HSQC NMR spectra with those from the model compounds. When comparing NMR data of phenol-acetylated versus phenol-etherified model compounds with those of acetylated lignins, it was apparent that most of the 4-O-5-linked structures in softwood lignins are present as free-phenolic end units.

In this work, we take advantage of the rod-like structure of electrosterically stabilized nanocrystalline cellulose (ENCC, with a width of about 7 nm and a length of about 130 nm), which has dicarboxylated cellulose (DCC) chains protruding from both ends, providing electrosterical stability for ENCC particles, to chemically end-to-end assemble these particles into nanocellulose fibers. ENCC with shorter DCC chains can be obtained by a mild hydrolysis of ENCC with HCl, and subsequently the hydrolyzed ENCC (HENCC, with a width of about 6 nm and a length of about 120 nm) is suitable to be assembled into high aspect ratio nanofibers by chemically cross-linking HENCC from one end to another. Two sets of HENCC were prepared by carbodiimide-mediated formation of an alkyne and an azide derivative, respectively. Cross-linking these two sets of HENCC was performed by a click reaction. HENCCs were also end-to-end cross-linked by a bioconjugation reaction, with a diamine. From atomic force microscopy (AFM) images, about ten HENCC nanoparticles were cross-linked and formed high aspect ratio nanofibers with a width of about 6 nm and a length of more than 1 μm.

Tunable erosion of polymeric materials is an important aspect of tissue engineering for reasons that include cell infiltration, controlled release of therapeutic agents, and ultimately to tissue healing. In general, the biological response to proteinaceous polymeric hydrogels is favorable (e.g., minimal inflammatory response). However, unlike synthetic polymers, achieving tunable erosion with natural materials is a challenge. Keratins are a class of intermediate filament proteins that can be obtained from several sources, including human hair, and have gained increasing levels of use in tissue engineering applications. An important characteristic of keratin proteins is the presence of a large number of cysteine residues. Two classes of keratins with different chemical properties can be obtained by varying the extraction techniques: (1) keratose by oxidative extraction and (2) kerateine by reductive extraction. Cysteine residues of keratose are "capped" by sulfonic acid and are unable to form covalent cross-links upon hydration, whereas cysteine residues of kerateine remain as sulfhydryl groups and spontaneously form covalent disulfide cross-links. Here, we describe a straightforward approach to fabricate keratin hydrogels with tunable rates of erosion by mixing keratose and kerateine. SEM imaging and mechanical testing of freeze-dried materials showed similar pore diameters and compressive moduli, respectively, for each keratose-kerateine mixture formulation (∼1200 kPa for freeze-dried materials and ∼1.5 kPa for hydrogels). However, the elastic modulus (G') determined by rheology varied in proportion with the keratose-kerateine ratios, as did the rate of hydrogel erosion and the release rate of thiol from the hydrogels. The variation in keratose-kerateine ratios also led to tunable control over release rates of recombinant human insulin-like growth factor 1.

Toward our goal of scalable, antimicrobial materials based on photodynamic inactivation, paper sheets comprised of photosensitizer-conjugated cellulose fibers were prepared using porphyrin and BODIPY photosensitizers, and characterized by spectroscopic (infrared, UV-vis diffuse reflectance, inductively coupled plasma optical emission) and physical (gel permeation chromatography, elemental, and thermal gravimetric analyses) methods. Antibacterial efficacy was evaluated against Staphylococcus aureus (ATCC-2913), vancomycin-resistant Enterococcus faecium (ATCC-2320), Acinetobacter baumannii (ATCC-19606), Pseudomonas aeruginosa (ATCC-9027), and Klebsiella pneumoniae (ATCC-2146). Our best results were achieved with a cationic porphyrin-paper conjugate, Por((+))-paper, with inactivation upon illumination (30 min, 65 ± 5 mW/cm(2), 400-700 nm) of all bacterial strains studied by 99.99+% (4 log units), regardless of taxonomic classification. Por((+))-paper also inactivated dengue-1 virus (>99.995%), influenza A (∼ 99.5%), and human adenovirus-5 (∼ 99%). These results demonstrate the potential of cellulose materials to serve as scalable scaffolds for anti-infective or self-sterilizing materials against both bacteria and viruses when employing a photodynamic inactivation mode of action.

The properties of paper sheets can be tuned by adjusting the surface or bulk chemistry using functional polymers that are applied during (online) or after (offline) papermaking processes. In particular, polymers are widely used to enhance the mechanical strength of the wet state of paper sheets. However, the mechanical strength depends not only on the chemical nature of the polymeric additives but also on the distribution of the polymer on and in the lignocellulosic paper. Here, we analyze the photochemical attachment and distribution of hydrophilic polydimethylacrylamide-co-methacrylate-benzophenone P(DMAA-co-MABP) copolymers with defined amounts of photoreactive benzophenone moieties in model paper sheets. Raman microscopy was used for the unambiguous identification of P(DMAA-co-MABP) and cellulose specific bands and thus the copolymer distribution within the cellulose matrix. Two-dimensional Raman spectral maps at the intersections of overlapping cellulose fibers document that the macromolecules only partially surround the cellulose fibers, favor to attach to the fiber surface, and connect the cellulose fibers at crossings. Moreover, the copolymer appears to accumulate preferentially in holes, vacancies, and dips on the cellulose fiber surface. Correlative brightfield, Raman, and confocal laser scanning microscopy finally reveal a reticular three-dimensional distribution of the polymer and show that the polymer is predominately deposited in regions of high capillarity (i.e., in proximity to fine cellulose fibrils). These data provide deeper insights into the effects of paper functionalization with a copolymer and aid in understanding how these agents ultimately influence the local and overall properties of paper.

Factors controlling the time-dependent mechanical properties of interpenetrating network (IPN) hydrogel materials are not well understood. In this study, alginate-polyacrylamide IPN were synthesized to mimic the stress relaxation behavior and elastic modulus of porcine muscle tissue. Hydrogel samples were created with single-parameter chemical concentration variations from a baseline formula to establish trends. The concentration of total monomer material had the largest effect on the elastic modulus, while concentration of the acrylamide cross-linker, N,N-methylenebis(acrylamide) (MBAA), changed the stress relaxation behavior most effectively. The IPN material was then tuned to mimic the mechanical response of muscle tissue using these trends. Swelling the hydrogel samples to equilibrium resulted in a dramatic decrease in both elastic modulus and stress relaxation behavior. Collectively, the results demonstrate that alginate-polyacrylamide IPN hydrogels can be tuned to closely mimic both the elastic and the viscoelastic behaviors of muscle tissue, although swelling detrimentally affects these desired properties.

In this work, flexible and free-standing composite films of nanofibrillated cellulose/polypyrrole (NFC/PPy) and NFC/PPy-silver nanoparticles (NFC/PPy-Ag) have been synthesized for the first time via in situ one-step chemical polymerization and applied in potential biomedical applications. Incorporation of NFC into PPy significantly improved its film formation ability resulting in composite materials with good mechanical and electrical properties. It is shown that the NFC/PPy-Ag composite films have strong inhibition effect against the growth of Gram-positive bacteria, e.g., Staphylococcus aureus. The electrical conductivity and strong antimicrobial activity makes it possible to use the silver composites in various applications aimed at biomedical treatments and diagnostics. Additionally, we report here the structural and morphological characterization of the composite materials with Fourier-transform infrared spectroscopy, atomic force microscopy, and scanning and transmission electron microscopy techniques.