In situ Synthesis of Single Layered Metal-Organic Frameworks via Inkjet Printing on a Cellulose Nanofiber Film.

The inkjet printing is a simple method to develop pattern-controlled 2D metal-organic frameworks (MOFs) due to its cost-effectiveness and ease of operation. Despite the sophisticated structures of MOF crystals, the MOF surfaces are easily contaminated by the adsorption of an ink solution, and the printing nozzle can be clogged by the aggregates of MOFs during printing. Unlike the mixture inks of MOFs and a carrier medium, the surface-specific patterning by in situ synthesis provides the film surface with the controlled patterns of an MOF single layer having different morphologies of MOFs without changing the ink cartridges. It enables facile printing due to the low viscosity of inks and escapes the risk of nozzle clogging because MOFs are synthesized at the printed patterns on the substrates. The ion-exchanged cellulose nanofiber (CNF) films form strong coordination with metal ions enhancing the stability of the MOFs on the film surface. It also demonstrates the controlled coverage of the MOFs by the printing pass number and the carboxylate content of CNF and the tunable adsorption of the guest molecules for different loading capacities of the printed patterns.

Enhanced Preservation of Climacteric Fruit with a Cellulose Nanofiber-Based Film Coating.

Bananas are a typical climacteric fruit with high respiration and ethylene production rates after harvest, and they show rapid ripening-senescence phenotypes. Here, we demonstrate that carboxymethylcellulose nanofibers (CM-CNFs) and red cabbage extracts (RCE) can be used as a unique film coating formulation for enhancement of the shelf-life of fruit. A CM-CNF suspension solution is created through a process involving chemical modification, followed by mechanical grinding. It has a high aspect ratio that allows for the creation of a thin and transparent film on the surface of bananas. The cross-linked CM-CNF hydrogel forms a dense film layer on the banana surface during dehydration and prevents respiration and weight loss. RCE contains polyphenols acting as antioxidants, which prevent the appearance of black dots on the banana peels. It serves to mitigate the browning of banana skins and also hinders the respiration process, consequently slowing the aging of bananas.

Hydrochromic film for dynamic information storage using cellulose nanofibers and silica nanoparticles.

A hydrochromic composite film was fabricated by incorporating silica nanoparticles (SiNPs) with cellulose nanofibers (CNFs). The CNF/SiNP composite film underwent a reversible change in transparency in response to external moisture variation. The CNFs improved the dimensional stability of the CNF/SiNP composite film and induced morphological differences in SiNP agglomerates, which control the water vapor condensation in a porous film. The condensed water in the pores reduced the difference in refractive index over the CNF/SiNP film, enhancing its transparency. The selective transparency of the composite film was challenged by printing CNF/SiNP inks at different composition ratios. The differing susceptibility of the printed patterns to moisture provided selective transparency at specific patterns, which can store dynamic information such as QR or numerical codes by simple water vapor adsorption and desorption.

Biophotovoltaic living hydrogel of an ion-crosslinked carboxymethylated cellulose nanofiber/alginate.

Due to the low electrical power generation in liquid cultures of photosynthetic microalgae, a solid medium culture is demanded for the efficient design of biophotovoltaic (BPV) cells. In particular, the conductivity of the culture medium and the contact of microalgae with an electrode are crucial in harvesting electrons in BPV cells. Here, an ion-crosslinked carboxymethylated cellulose nanofiber (CM-CNF)/alginate is proposed as a living hydrogel for the green power generation of Chlorella vulgaris embedded in the hydrogel. The hydrogel crosslinked with Ca2+ and Fe3+ ions showed more efficient BPV properties than the hydrogel crosslinked with only Ca2+ due to the increase of conductivity. The efficient transport of electrons generated by C. vulgaris improves the power generation of BPV cells. Moreover, the fluid channels imprinted in the living hydrogel maintain the viability of C. vulgaris even under the ambient environment by preventing the solid medium from being dried out.

Embedded Direct Ink Writing 3D Printing of UV Curable Resin/Sepiolite Composites with Nano Orientation.

Among the various 3D printing methods, direct ink writing (DIW) through extrusion directly affects the microstructure and properties of materials. However, use of nanoparticles at high concentrations is restricted due to difficulties in sufficient dispersion and the deteriorated physical properties of nanocomposites. Thus, although there are many studies on filler alignment with high-viscosity materials with a weight fraction higher than 20 wt %, not much research has been done with low-viscosity nanocomposites with less than 5 phr. Interestingly, the alignment of anisotropic particles improves the physical properties of the nanocomposite at a low concentration of nanoparticles with DIW. The rheological behavior of ink is affected by the alignment of anisotropic sepiolite (SEP) at a low concentration using the embedded 3D printing method, and silicone oil complexed with fumed silica is used as a printing matrix. A significant increase in mechanical properties is expected compared to conventional digital light processing. We clarify the synergistic effect of the SEP alignment in a photocurable nanocomposite material through physical property investigations.

Matrix-Assisted In Situ Polymerization of a 3D Conductive Hydrogel Structure.

It is challenging to fabricate 3D architectures of conductive hydrogels and impart uniform conductivity at the same time. Here, we demonstrate a one-step 3D printing technique for controlling the 3D structure of hydrogel materials while simultaneously conferring uniform conductivity. The core technology lies in the in situ polymerization of conductive polymers by the diffusion of monomers and redox initiators to an interface. An alginate ink containing ammonium peroxide as a redox initiator is printed in a silica nanoparticle matrix containing a pyrrole monomer. A 3D structure of conductive polypyrrole is uniformly fabricated on the surface of the alginate immediately after the printing. This simple process provides uniform electrical conductivity throughout the bulk structure.

Free-form three-dimensional nanocellulose structure reinforced with poly(vinyl alcohol) using freeze-thaw process.

The free-form fabrication of networked bacterial cellulose (BC) structures was available using a particle matrix and a bioink embedding bacteria. However, the mechanical strength of such BC hydrogel structures does not satisfy the requirements for biomedical applications that require high toughness and elasticity. Here, we adopt the freeze-thaw process with a water-soluble polymer to form a crystalline structure around the BC nanofibers. The crystallization of polymer chains such as poly(vinyl alcohol) (PVA) occurs spontaneously during this process, which results in the unique and environment-friendly methodology of the composition. Crystallization enhances the mechanical strength of free-form BC hydrogels by filling the space between the nanofiber networks with crystalline polymeric fillers. Uniquely, a simple morphological variation can improve the mechanical strengths of BC/PVA cryogels, and this process may be broadly applicable as a tool for biomaterial design and fabrication.

Mimicry of the plant leaf with a living hydrogel sheet of cellulose nanofibers.

Here, we composite an artificial leaf comprising a transparent hydrogel sheet, vein structures, and a photosynthetic system using cellulose nanofibers (CNFs) which can be produced from a biomass. A simple imprinting using a 3D printed stamp enabled the formation of fluidic channels in the hydrogel, embedding living cells without toxic chemistry or a drying process. Microalgae in the hydrogel grows and proliferates under ambient condition for a long period because of the continuous supply of nutrient from the channels, which is more effective for metabolic bioactivity than a flat sheet cultured in a bulk solution. This mimicry of the plant leaf provides a potential for a whole artificial plant. In addition, the simple fabrication of fluidic channels in the hydrogel can be applied to diverse living organisms, including bacteria, animal, and plant cells.

Soft Magnetostrictive Actuator String with Cellulose Nanofiber Skin.

The formation of cellulose nanofibrous skin with a colloidal suspension is challenging due to the diffusion of colloidal particles and bacteria to the bulk and a limited supply of oxygen for bacteria in the liquid culture environment. A composite-actuating string was fabricated with magnetic nanoparticles (MNPs) and Gluconacetobacter xylinus in a solid matrix of hydrophobic microparticles. G. xylinus synthesizes a dense skin layer of cellulose nanofibers enclosing MNPs in the solid matrix to form an actuator string responsive to an external magnetic field. The nanofibrous actuator string is transformable to fit the diverse shapes of tubular structures in cross section due to its softness and plastic deformability, which reduce friction and stress against the walls of organ tissues. The nanofibrous skin string is bendable at an acute angle by magnetic actuation and is applicable as an endoscopic guidewire to reach a target deep inside a model kidney structure.

Development of cellulose nanocrystal-stabilized Pickering emulsions of massoia and nutmeg essential oils for the control of Aedes albopictus.

We investigated the larvicidal potential of 10 plant essential oils (EOs) against the Asian tiger mosquito Aedes albopictus. Among the EOs, larvicidal activity against Ae. albopictus was strongest in those derived from massoia (Massoia aromatica) and nutmeg (Myristica fragrans). Larvicidal activities of massoia and nutmeg EOs against Ae. albopictus were 95.0% and 85.0% at 50 µg/mL, respectively. A total of 4 and 14 compounds were identified from massoia and nutmeg, respectively, and two massoia lactones, C10 and C12, were isolated from massoia EO. Among the identified compounds, benzyl salicylate, terpinolene, C12 massoia lactone, sabinene, benzyl benzoate, methyl eugenol, and C10 massoia lactone exhibited the strong larvicidal activity. Cellulose nanocrystal (CNC)-stabilized Pickering emulsions of massoia and nutmeg EOs were developed to overcome the insolubility of EOs in water. CNC/massoia and CNC/nutmeg emulsions were stable for at least 10 days, and larvicidal activities of CNC/massoia PE and CNC/nutmeg were higher than those of crude massoia and nutmeg EOs. This study presents a CNC-stabilized PE, a suitable formulation for EOs, as a potential larvicide against Ae. albopictus.

Rheological properties of cellulose nanofiber hydrogel for high-fidelity 3D printing.

Optimization of the rheological properties of the matrix is ​​critical for high-fidelity matrix-assisted 3D printing (MAP), which enables the free-form fabrication of fluidic soft materials. This report describes the generic criteria observable in the printing process of cellulose nanofiber (CNF) hydrogels: the sharpness of an angled line, the cross-sectional ratio of a feature, the surface roughness of features, and the completeness of multi-line writing. The concentration and physical properties of the CNF affects the printing fidelity by changing the values of the four criteria, which are closely related to the rheological properties of the matrix. The printing fidelity can be enhanced by the optimal combination of the inks and the CNF matrix. Hydrophilic and hydrophobic inks are printed in the CNF matrix demonstrating as a universal matrix for free-form fabrication with liquid inks.

Protective coating of strawberries with cellulose nanofibers.

Since shelf life of perishable foods is short, a compelling challenge is to prolong the freshness of foods with a cost-effective strategy. A perishable fruit, the strawberry, is chosen as a model perishable food and an edible film coating is applied to it using carboxymethylated cellulose nanofibers (CM-CNFs) stabilized by cationic salts. A transparent and impermeable CM-CNF film is formed at the strawberry surface using a dip coating process. The formation of the film is dependent on the electrostatic interaction between anionic CM-CNF and salt cations. Physical properties of the film are characterized and the effectiveness of edible film coating on the freshness of perishable fruit is evaluated by the measurement of weight loss, CO2 release, firmness, total solid sugar and acidity. Cellulose nanofiber is a promising cost-effective material appropriate for use as an edible coating that contributes to the long-term storage and prolonged freshness of foods.

Larvicidal composite alginate hydrogel combined with a Pickering emulsion of essential oil.

Sulfonated cellulose nanocrystals (S-CNCs) can be used to encapsulate thyme white essential oil (EO) that is volatile and immiscible with water. S-CNCs form a Pickering emulsion (PE) with EOs and the micron-scale PEs are embedded in sodium alginate (SA) to form macroscale hydrogel beads. The incorporation of PEs with SA is confirmed with FTIR, XRD, SEM and confocal microscopic characterizations and the release behavior is monitored to understand the time-dependent biological activity of the EOs. The larvicidal performance of the SA-PE composite hydrogel beads is investigated with Aedes albopictus (Skuse) larvae. The larvicidal activity is higher for SA/PE hydrogel beads prepared at 0.5 % CaCl2 than 0.75 or 1.0 % CaCl2 due to their higher release rate.

3D structure of lightweight, conductive cellulose nanofiber foam.

We investigate the three-dimensional (3D) structuring of cellulose nanofiber (CNF) foam-based ink using direct ink writing 3D printing and the transformation of CNF foam from an insulator to a conductor. The colloidal stability of a CNF foam is critical to producing a solid CNF foam which can be used as a template for the synthesis of conducting polymers. Liquid CNF foam ink is produced by simple stirring of CNF suspension with sodium dodecyl sulfate as an emulsifier. The shear thinning behavior of the liquid CNF foam ink enables printing through a needle. Flexible design of CNF foam structures is enabled by 3D printing using computer-aided design. Lightweight conductive CNF foams are prepared via in situ polymerization of polypyrrole on a solid CNF foam. The topological features of the resultant porous conductive CNF foams are observed, and their conductivity is investigated.

3D Printing of Polyethylene Terephthalate Glycol-Sepiolite Composites with Nanoscale Orientation.

A fused-deposition modeling (FDM) 3D-printed polyethylene terephthalate glycol (PETG)-sepiolite composite showed effective synergetic mechanical reinforcement in tensile testing compared to an injection-molded composite. The results showed that the addition of 3 phr sepiolite improved the tensile strength of 3D-printed PETG samples by 35.4%, while the tensile strength of injection-molded PETG samples was improved by 7.2%. To confirm these phenomena, FDM PETG-sepiolite composites were investigated by small-angle X-ray scattering to correlate the nanostructures of the composites with their mechanical strengths. The small-angle X-ray scattering data and transmission electron microscopy observations demonstrated that needle-shaped sepiolite particles were aligned in the printing direction. This fine oriented nanostructure formed during 3D printing created a synergistic effect that improved the material properties of the composite. These novel PETG-sepiolite composites with enhanced mechanical properties can be promising materials fabricated via FDM 3D printing.

Biological Activity of Thyme White Essential Oil Stabilized by Cellulose Nanocrystals.

Cellulose nanocrystals (CNCs) are produced by sulfonic acid hydrolysis and used for the formation of Pickering emulsion (PE) with thyme white essential oil (EO). Highly volatile and hydrophobic thyme white is encapsulated in PE by the amphiphilicity of CNCs. Encapsulation of EO in a CNC shell is determined by confocal microscopy with distinct fluorescent labelling. The amount of CNC affects the size distribution of PE, and the emulsion stability is confirmed by rheological property. The antimicrobial activity of the emulsion is evaluated against Escherichia coli and Staphylococcus aureus by minimal inhibitory concentration and minimum bactericidal concentration. The larvicidal activity is also investigated against Aedes albopictus by dispersing the emulsion in water.

Solid matrix-assisted printing for three-dimensional structuring of a viscoelastic medium surface.

Gluconacetobacter xylinus (G. xylinus) metabolism is activated by oxygen, which makes the formation of an air-medium interface critical. Here we report solid matrix-assisted 3D printing (SMAP) of an incubation medium surface and the 3D fabrication of bacterial cellulose (BC) hydrogels by in situ biosynthesis of G. xylinus. A printing matrix of polytetrafluoroethylene (PTFE) microparticles and a hydrogel ink containing an incubation medium, bacteria, and cellulose nanofibers (CNFs) are used in the SMAP process. The hydrogel ink can be printed in the solid matrix with control over the topology and dimensional stability. Furthermore, bioactive bacteria produce BC hydrogels at the surface of the medium due to the permeability of oxygen through the PTFE microparticle layer. The flexibility of the design is verified by fabricating complex 3D structures that were not reported previously. The resulting tubular BC structures suggest future biomedical applications, such as artificial blood vessels and engineered vascular tissue scaffolding. The fabrication of a versatile free-form structure of BC has been challenged due to restricted oxygen supplies at the medium and the dimensional instability of hydrogel printing. SMAP is a solution to the problem of fabricating free-form biopolymer structures, providing both printability and design diversity.

Transparent cellulose nanofiber based open cell culture platform using matrix-assisted 3D printing.

Carboxymethylated hydrophilic CNF (Hphil-CNF) was modified with methyltrimethoxysilane into hydrophobic CNF (Hphob-CNF) and used as a printing matrix. The Hphil-CNF hydrogel was printed at the surface of the Hphob-CNF hydrogel, forming an immiscible, distinct 3D structure. Fabrication of channel systems in the CNF platform was performed by matrix-assisted 3D printing of petroleum jelly ink in the Hphil-CNF-patterned Hphob-CNF hydrogel. After the dehydration process followed by removal of the ink from the CNF film, the CNF hydrogels became a dense platform embedding fluidic channels. The CNF platform exhibited selective diffusion of fluorescein isothiocyanate-dextran from the channels in the Hphil-CNF patterns, indicating transport of bioactive molecules to cells cultured at the platform surface. The applicability of the open cell culture platform was investigated with A549 lung cancer cells by injecting cisplatin, a model drug into the channel.

pH-Triggered Silk Fibroin/Alginate Structures Fabricated in Aqueous Two-Phase System.

An aqueous two-phase system (ATPS) is a water-in-water biphasic system, which is generally formed by two incompatible polymers. Recently, considerable effort has been dedicated to search for new ATPS polymer pairs to further expand ATPS's applications. In this paper, a new ATPS system based on silk fibroin (SF) and alginate is introduced. A phase diagram was established to show the critical concentrations for the formation of an SF/alginate ATPS. The present system is sensitive to pH stimulus and transformed from an ATPS into a single-phasic system as pH increases above ∼9.5. Circular dichroism, fluorescence emission spectra, hydrodynamic diameter, and ζ-potential data together indicate that the SF chains undergo a dramatic extension as pH is increased, which is the reason underlying the pH-triggered phase transition. As feasible applications of this biphasic system, compartmentalized multiplex immunoassay, controlled encapsulation and release, and hierarchical fiber fabrication were demonstrated using the SF/alginate ATPS.

Melanin Nanoparticle-Incorporated Silk Fibroin Hydrogels for the Enhancement of Printing Resolution in 3D-Projection Stereolithography of Poly(ethylene glycol)-Tetraacrylate Bio-ink.

It is not easy to design structures with transparent solutions, especially in light projection three-dimensional (3D) printing, since the penetration of light in solution is limitless. Here, silk fibroin incorporated with melanin nanoparticles (SFM) is used as a transparency modifier of poly(ethylene glycol)-tetraacrylate (PEG4A) solution. The incorporation of melanin into the SF hydrogel is performed in the range of 0.05-0.2% (w/v), and the SFM was added to the PEG4A precursor solution at 0.25-1.0% (w/v). The printing accuracy was examined by comparing the printed and designed feature sizes. The addition of 1.0% (w/v) SFM to a 4% (w/v) PEG4A (PEG4A/SFM) precursor solution effectively reduces the transparency of the solution and improves the printing resolution by confining the light beam to a designed region. This enables the fabrication of hard-to-express features such as hollow blood vessels or vacant tubes. Furthermore, the elastic modulus of the printed PEG4A/SFM composite hydrogel increases 2.5-fold higher than the PEG4A hydrogel without SFM. For the bio-ink, PEG4A/SFM-containing cells show non-cytotoxicity and improve the proliferation rate of embedded cells, confirming the high biocompatibility of PEG4A/SFM hydrogels.