• Macromolecular Research
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• v.16 no.6
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• pp.539-543
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• 2008

Many natural proteins self-assemble in complex ways, either to fulfill their biological function or introduce particular properties, such as high strength and toughness. We report the morphological transition in water from a spherical to rod-like shape of Bombyx mori silk fibroin by reducing the pH. Transmission electron microscopy, scanning electron microscopy, and dynamic light scattering were used to characterize the dilute solutions of silk fibroin in an aqueous environment, and provide direct visualization of the transformation of spherical micelles at pH 6.8 to nanofibrils at pH 4.8. This change in morphology occurred as a result of the stretching entropy due to the formation of $\beta$-sheets, which was analyzed using circular dichroism spectroscopy. This study demonstrates the self-assembly of silk fibroin as a function of pH.

• Applied Chemistry for Engineering
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• v.32 no.1
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• pp.110-116
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• 2021

In this work, the surface of hydrophilic cellulose nanofibrils (CNFs) was modified precisely by varying amounts of cetyltrimethylammonium bromide (CTAB) to produce CNF-based particle surfactants. We found that a critical CTAB density was required to generate amphiphilic CTAB-grafted CNF (CNF-CTAB). Compared to pristine CNF, CNF-CTAB was highly efficient at stabilizing oil-in-water Pickering emulsions. To evaluate their effectiveness as particle surfactants, the surface coverage of oil-in-water emulsion droplets was determined by changing the CNF-CTAB concentration in the aqueous phase. Furthermore, styrene-in-water stabilized by CNF-CTAB surfactants was thermally polymerized to produce CNF-stabilized polystyrene (PS) particles, offering a great potential for various applications including pharmaceuticals, cosmetics, and petrochemicals.

• International Journal of Industrial Entomology and Biomaterials
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• v.45 no.2
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• pp.70-77
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• 2022

Wet-spun regenerated silk fibroin (RSF) fibers have been extensively studied owing to their 1) useful properties as biomaterials, including good blood compatibility and cyto-compatibility; 2) the various methods available to control the structural characteristics and morphology of the fiber, and 3) the possibility of fabricating blended fibers and new material-embedded fibers. In this study, silk nanofibrils prepared using a new method were embedded in RSF to fabricate wet-spun silk nanofibril/RSF composite fibers. Up to 2% addition of silk nanofibril, the silk nanofibril/RSF dope solution showed slight shear thinning, and the G' and G" of the dope solution were similar. However, above 3% silk nanofibril content, the viscosity of the dope solution significantly increased. In addition, shear thinning was remarkably evident, and the G' of the dope solution was much higher than the G", indicating a very elastic state. As the silk nanofibril content was increased, the wet-spun silk nanofibril/RSF composite fiber became uneven, with a rough surface, and more beaded fibers were produced. Scanning electron microscopy observations revealed that the beaded fibers were attributed to the inhomogeneous dispersion and presence of agglomerates of the silk nanofibrils. As the silk nanofibril content and RSF concentration increased, the maximum draw ratio decreased, indicating the deterioration of the wet spinnability and post-drawing performance of silk nanofibril/RSF.

• Journal of the Korean Wood Science and Technology
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• v.50 no.6
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• pp.436-447
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• 2022

Lignocellulose nanofibrils (LCNFs) were prepared using a two-step deep eutectic solvent (DES) and enzymatic pretreatment followed by mechanical defibrillation, and we examined the effects of enzymatic pretreatment conditions on different characteristics of the LCNFs thus obtained. The LCNFs yielded using the two-step DES pretreatment (Enz-LCNF) exhibited a well-defibrillated entangled web-like structure with an average fiber diameter ranging from 15.7 to 20.4 nm. Furthermore, we found that the average diameter and filtration time of the Enz-LCNFs decreased with an increase in enzyme concentration and enzymatic treatment time, whereas we detected a concomitant reduction in the tensile strength of the Enz-LCNF sheets. The Enz-LCNFs were characterized by a typical cellulose I structure, thereby indicating that the enzymatic treatment causes very little damage to the crystalline form.

• Journal of the Korean Wood Science and Technology
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• v.39 no.3
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• pp.197-205
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• 2011

Cellulose nanofibrils (CNF) with 50~100 nm diameter were manufactured from micro-size cellulose by an application of a high-pressure homogenizer at 1,400 bar. High strength nanopapers were prepared over a filter paper by a vacuum filtration from CNF suspension. After reinforcing and dispersing CNF suspension, hydroxypropyl cellulose (HPC) and polyvinyl alcohol (PVA)-based composites were tailored by solvent- and film-casting methods, respectively. After 2, 4, 6 and 8 passes through high-pressure homogenizer, the tensile strength of the nanopapers were extremely high and increased linearly depending upon the pass number. Chemical modification of 1H, 1H, 2H, 2H-perfluorodecyl-triethoxysilane (PFDTES) on the nanopapers significantly increased the mechanical strength and water repellency. The reinforcement of 1, 3, and 5 wt% CNF to HPC and PVA resins also improved the mechanical properties of the both composites.

• Toxicological Research
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• v.35 no.1
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• pp.45-63
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• 2019

In view of the growing industrial use of Bacterial cellulose (BC), and taking into account that it might become airborne and be inhaled after industrial processing, assessing its potential pulmonary toxic effects assumes high relevance. In this work, the murine model was used to assess the effects of exposure to respirable BC nanofibrils (nBC), obtained by disintegration of BC produced by Komagataeibacter hansenii. Murine bone marrow-derived macrophages ($BMM{\Phi}$) were treated with different doses of nBC (0.02 and 0.2 mg/mL, respectively 1 and $10{\mu}g$ of fibrils) in absence or presence of 0.2% Carboxymethyl Cellulose (nBCMC). Furthermore, mice were instilled intratracheally with nBC or nBCMC at different concentrations and at different time-points and analyzed up to 6 months after treatments. Microcrystaline $Avicel-plus^{(R)}$ CM 2159, a plant-derived cellulose, was used for comparison. Markers of cellular damage (lactate dehydrogenase release and total protein) and oxidative stress (hydrogen peroxidase, reduced glutathione, lipid peroxidation and glutathione peroxidase activity) as well presence of inflammatory cells were evaluated in brochoalveolar lavage (BAL) fluids. Histological analysis of lungs, heart and liver tissues was also performed. BAL analysis showed that exposure to nBCMC or CMC did not induce major alterations in the assessed markers of cell damage, oxidative stress or inflammatory cell numbers in BAL fluid over time, even following cumulative treatments. $Avicel-plus^{(R)}$ CM 2159 significantly increased LDH release, detected 3 months after 4 weekly administrations. However, histological results revealed a chronic inflammatory response and tissue alterations, being hypertrophy of pulmonary arteries (observed 3 months after nBCMC treatment) of particular concern. These histological alterations remained after 6 months in animals treated with nBC, possibly due to foreign body reaction and the organism's inability to remove the fibers. Overall, despite being a safe and biocompatible biomaterial, BC-derived nanofibrils inhalation may lead to lung pathology and pose significant health risks.

• International Journal of Industrial Entomology and Biomaterials
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• v.26 no.2
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• pp.81-88
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• 2013

Wet-spun silk fibers have attracted the attention of many researchers because of 1) the unique properties of silk as a biomaterial, including good biocompatibility and cyto-compatability and 2) the various methods available to control the structure and properties of the fiber. Cellulose nanofibrils (CNFs) have typically been used as a reinforcing material for natural and synthetic polymers. In this study, CNF-embedded silk fibroin (SF) nanocomposite fibers were prepared for the first time. The effects of CNF content on the rheology of the dope solution and the characteristics of wet-spun CNF/SF composite fibers were also examined. A 5% SF formic acid solution that contained no CNFs showed nearly Newtonian fluid behavior, with slight shear thinning. However, after the addition of 1% CNFs, the viscosity of the dope solution increased significantly, and apparent shear thinning was observed. The maximum draw ratio of the CNF/SF composite fibers decreased as the CNF content increased. Interestingly, the crystallinity index for the silk in the CNF/SF fibers was sequentially reduced as the CNF content was increased. This phenomenon may be due to the fact that the CNFs prevent ${\beta}$-sheet crystallization of the SF by elimination of formic acid from the dope solution during the coagulation process. The CNF/SF composite fibers displayed a relatively smooth surface with stripes, at low magnification (${\times}500$). However, a rugged nanoscale surface was observed at high magnification (${\times}10,000$), and the surface roughness increased with the CNF content.

• Applied Chemistry for Engineering
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• v.27 no.4
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• pp.380-385
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• 2016

Nanocelluloses, mainly cellulose nanofibrils (CNF) and cellulose nanocrystals (CNC, i.e., defect-free, rod-like crystalline residues after acid hydrolysis of fibers), have been the subject of recent interest. Due to the presence of hydroxyl groups on the surface of nanocelluloses, their surfaces are reactive, making them suitable candidates for reinforcing materials for manufacturing polymer composites. In this study, CNF was used as a reinforcing material for manufacturing cement composites. CNF was prepared by TEMPO (2,2,6,6,-tetramethyl piperidine-1-oxyl radical) oxidation procedure combined with extensive homogenization and ultrasonication. Transmission electron microscopy (TEM) analysis of the suspension showed the width of CNF between 10 and 15 nm. The compressive strength of cement composites containing 0.5% CNF was comparable to that of conventional cement composites. On the other hand, the tensile and flexural strength were improved by 49.7% and 38.8%, respectively, compared to those of conventional cement composites. Also, at an ambient condition, the degree of self-shrinkage reduction reached to 18.9% in one day, followed by 5.9% in 28 days after molding.

• Journal of the Korean Wood Science and Technology
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• v.45 no.3
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• pp.268-277
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• 2017

In this study, lignocellulose nanofibrils (LCNFs) were prepared from Pussy willow wood powder by disk-milling after pretreatment using the cosolvent of 1-ethyl-3-methylimidazolium acetate ([EMIM]Ac) and N,N-dimethylformamide (DMF) with different mixing ratios for different time. All pretreated samples showed native cellulose I polymorph and cellulose crystallinity was lowest when cosolvent of DMF with 30% [EMIM]Ac was used. Average crystallite size of raw material and the pretreated product by MDF and its cosolvent with 10% [EMIM]Ac was found to be about 3.2 nm and decreased with increasing pretreatment time at the DMF cosolvent with 30% [EMIM]Ac. Defibrillation efficiency was improved by loosening wood cell wall structure by the pretreatment using co-solvent system of [EMIM]Ac and DMF.

• Proceedings of the Korean Vacuum Society Conference
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• 2010.02a
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• pp.397-397
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• 2010

Bone is considered as hierarchically organized biocomposites of organic (collagen) and inorganic (hydroxyapatite) materials. The precise structural dependence between hydroxyapatite (HAp, $Ca_{10}(PO_4)_6(OH)_2)$ crystals and collagen fibril is critical to unique characteristics of bone. To meet those conditions and obtain optimal properties, it is essential to understand and control the initial growth mechanisms of hydroxyapatite at the molecular level, such as other nano-structured materials. In this study, collagen fibrils were prepared by adsorbing native type I collagen molecules onto hydrophobic surface. Hydrophobicity was introduced on the Si wafer surface by using PECVD (plasma enhanced chemical vapor deposition) method and cyclohexane as a precursor. Biomimetic nucleation and growth of HAp on the self-assembled collagen nanofibrils were occurred through incubation of the sample in SBF (simulated body fluid). Chemical and morphological evolution of HAp nanocrystals was investigated by surface-sensitive analytical techniques such as ToF-SIMS (Time-of-Flight Secondary Ion Mass Spectrometry) and AFM (Atomic Force Microscopy) in the early growth stages (< 24 hrs). The very initial stages (< 12 hrs) of mineralization could be clearly demonstrated by ToF-SIMS chemical mapping of surface. In addition to ToF-SIMS and AFM measurement, scanning electron microscopy, energy dispersive spectroscopy and X-ray diffraction analysis were conducted to characterize the HAp layer in the late stages. This study is of great importance in the growth of real bone-like materials with a structure analogous to that of natural bones and the development of biomimetic nanomaterials.