TEMPO-oxidized Bacterial Cellulose Research Articles

Controlled Sol-Gel Transitions of Metal-Organic Membrane-Enveloped Cellulose Nanofibrils via Metal Coordination in Aqueous Media.

We report a metal coordination-driven sol-gel transition system where cellulose nanofibrils are enveloped by a rationally designed metal-organic membrane (MOM) in an aqueous medium. Specifically, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized bacterial cellulose (TOBC) is encapsulated within an MOM comprising Zn2+ and the chelator phytic acid (PA), denoted TOBCMOM. Using the DLVO theory, we elucidate how tuning the metal ion valence in TOBCMOM modulates the sol-gel transition by controlling interfibrillar attractive forces. Notably, TOBCMOM fluids exhibit relaxation times consistent with the Kohlrausch-Williams-Watts (KWW) function. Significantly, we demonstrate reversible, sustainable sol-gel transitions in TOBCMOM under stepwise mechanical strain. This facile approach enables rheological tailoring of aqueous media, promising for the development of advanced stimuli-responsive smart fluids for applications in cosmetics, food science, and pharmaceutical formulations.

Effect of TEMPO-oxidized bacterial cellulose nanofibers stabilized Pickering emulsion of cinnamon essential oil on structure and properties of gelatin composite films

Pure gelatin film often exhibits high hydrophilicity and a lack of antibacterial activity, hindering its practical application in the field of food preservation. To address these issues, we incorporated 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized bacterial cellulose (TOBC) nanofibers stabilized cinnamon essential oil (CEO) Pickering emulsions into the gelatin matrix to develop active food packaging films. The study revealed that the good distribution of emulsion droplets in the film matrix. While with increasing Pickering emulsion proportion, the microstructures of composite films were more heterogeneous, showing some pores or cavities. In addition, the insertion of TOBC-stabilized CEO emulsions could improve the elongation at break (EAB), water-resistance, UV blocking ability, and antibacterial activity of film, but reduced its tensile strength (TS) and water vapor barrier properties (WVP). Notably, the film prepared with 4 % TOBC-stabilized CEO Pickering emulsion demonstrated enhanced preservation of strawberries. Overall, the as-prepared gelatin-based active composite films have considerable potential for food packaging.

Comparative Analysis of the Influence of Different Preparation Methods on the Properties of TEMPO-Oxidized Bacterial Cellulose Powder Films

ABSTRACT The preparation method of cellulose films plays a vital role in their properties. This work aims to characterize 2, 2, 6, 6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized bacterial cellulose powder (TOBCP) films prepared with three different methods (casting, boiling-casting, and boiling-vacuum). It is found that film by casting (CT film) shows the best electrical properties. A light-emitting diode (LED) in a direct current circuit connected to the CT film glows the most brightly. However, this film had lower tensile strength and thermal stability than films from boiling and boiling-vacuum techniques. The boiling-vacuum film presents the most compact fiber structure and the highest tensile and thermal properties. This film also shows the lowest electrical properties and the dimmest LED light. These results demonstrate the TOBCP properties from different methods that can be used to prepare film with desirable properties.

Preparation and assessment of agar/TEMPO-oxidized bacterial cellulose cryogels for hemostatic applications.

In this work, we have demonstrated agar and oxidized bacterial cellulose cryogels as a potential hemostatic dressing material. TEMPO-oxidized bacterial cellulose (OBC) was incorporated into the agar matrix, improving its mechanical and hemostatic properties. The oxidation of bacterial cellulose (BC) was evidenced by chemical characterization studies, confirming the presence of carboxyl groups. The in vitro blood clotting test conducted on agar/OBC composite cryogels demonstrated complete blood clotting within 90 seconds, indicating their excellent hemostatic efficacy. The cryogels exhibited superabsorbent properties with a swelling degree of 4200%, enabling them to absorb large amounts of blood. Moreover, the compressive strength of the composite cryogels was appreciably improved compared to pure agar, resulting in a more stable physical structure. The platelet adhesion test proved the significant ability of the composite cryogels to adhere to and aggregate platelets. Hemocompatibility and cytocompatibility tests have verified the safety of these cryogels for hemostatic applications. Finally, the material exhibited remarkable in vivo hemostatic performance, achieving clotting times of 64 seconds and 35 seconds when tested in the rat tail amputation model and the liver puncture model, respectively. The experiment results were compared with those of commercial hemostat, Axiostat, and Surgispon, affirming the potential of agar/OBC composite cryogel as a hemostatic dressing material.

Enhanced properties of TEMPO-oxidized bacterial cellulose films via eco-friendly non-pressurized hot water vapor treatment for sustainable and smart food packaging.

Developing a simple and environmentally friendly method to vary the physical, mechanical, and thermal properties of cellulose films is of great importance. This study aimed to characterize 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO)-oxidized bacterial cellulose (BC) films prepared using non-pressurized hot water vapor (NPHWV) method. A wet BC-pellicle that had been oxidized with TEMPO was treated with NPHWV for 60, 120, and 240 minutes, respectively. As a control, a TEMPO-oxidized BC (TOBC) film without NPHWV was prepared. The results show that the longer NPHWV duration of the TOBC film increased the tensile and thermal properties. This film became more hydrophobic and showed lower moisture absorption, thermal conductivity and organic solvent uptake, more crystalline structure, and higher fiber density after NPHWV treatment. The acquired results provide a simple, inexpensive, and ecologically friendly method for varying TOBC film properties.

Cinnamon essential oil Pickering emulsions: Stabilization by bacterial cellulose nanofibrils and applications for active packaging films

Pickering emulsions are emulsions stabilized by solid particles with a wide range of potential applications as they typically provide more stable systems than surface-stabilized emulsions. Among the various solid stabilizers, bacterial cellulose (BC) may open up new opportunities for future Pickering emulsions due to its unique nano-size, amphiphilicity and other excellent properties. In this study, BC, TEMPO-oxidized BC (TOBC) and dialdehyde cellulose (DAC) were used as emulsifiers to stabilize cinnamon essential oil (CEO) Pickering emulsions. The microstructure, oil droplet size distribution, storage and loss moduli of the Pickering emulsions were affected by the type of emulsifier used. Compared to BC and DAC nanofibers, TOBC nanofibers exhibited better emulsifying capacity. TOBC (1%)-stabilized Pickering emulsion showed smaller droplet size, narrower size distributions, better stability and sustained release ability. Moreover, the Pickering emulsions showed high antibacterial activities against Gram-positive bacteria S. aureus and Gram-negative bacteria E. coli. Active gelatin composite films containing TOBC (1%)-stabilized CEO Pickering emulsions were successfully fabricated and showed good antibacterial and antioxidant properties, which make them suitable for food packaging application.

Cu-vitamin B3 donut-like MOFs incorporated into TEMPO-oxidized bacterial cellulose nanofibers for wound healing

In this study, a novel multifunctional nanocomposite wound dressing was developed, consisting of TEMPO-oxidized bacterial cellulose (TOBC) nanofibers functionalized with donut-like copper-based metal–organic frameworks (CuVB3 MOFs). These CuVB3 MOFs were constructed using copper nodes linked by vitamin B3 molecules, resulting in a copper nicotinate crystal structure as confirmed by X-ray diffraction. Electron microscopy confirmed the presence of donut-like microstructures with uniform element distribution in the synthesized MOFs. Through the incorporation of CuVB3 MOFs into the TOBC nanofibers, innovative TOBC-CuVB3 nanocomposites were created. Biocompatibility testing using the MTT assay demonstrated enhanced cell viability of over 115% for the TOBC-CuVB3 nanocomposite. Acridine Orange staining revealed a ratio of 88–92% live cells on the wound dressings. Furthermore, fibroblast cells cultured on TOBC-CuVB3 exhibited expanded morphologies with long filopodia. The agar diffusion method exhibited improved antibacterial activity against both Gram-positive and Gram-negative bacterial strains, correlating with increased CuVB3 concentration in the samples. In vitro cellular scratch assays demonstrated excellent wound healing potential, with a closure rate of over 98% for wounds treated with the TOBC-CuVB3 nanocomposite. These findings underscore the synergistic effects of copper, vitamin B3, and TOBC nanofibers in the wound healing process.

Enhanced UV blocking, tensile and thermal properties of bendable TEMPO-oxidized bacterial cellulose powder-based films immersed in PVA/Uncaria gambir/ZnO solution

The production of UV-resistant films from biomaterials is currently an active field of research. ZnO nanoparticle polymer fillers have been found to improve UV-light opacity. However, using ZnO as a filler is relatively expensive and time-consuming for film preparation. Substituting some of the ZnO nanoparticles with Uncaria gambir extract has been suggested to reduce the cost of film production, as the phenolic hydroxyl group present in Uncaria gambir provides excellent UV resistance. This study characterized dry bacterial cellulose (BC) powder-based films immersed without and with polyvinyl alcohol/Uncaria gambir extract/ZnO (M) solution for 2 and 5 min. It was found that BC/M biocomposites blocked 100% of the UV light while remaining transparent to visible wavelengths. These bendable biocomposite films also presented high tensile and thermal resistance properties. Immersion for 5 min increased significantly tensile strength, elongation at break, and toughness of the biocomposite to 77.2 MPa, 12.3%, and 5.8 MJ/m3, an increase of 130%, 748%, and 2409%, respectively, compared to uncoated BC film. These results suggest the immersion method could provide more efficient, environmentally friendly biocomposite films with significant UV resistance.

Growth of spiral ganglion neurons induced by graphene oxide/oxidized bacterial cellulose composite hydrogel

The damage or degeneration of spiral ganglion neurons (SGNs) can impair the auditory signals transduction from hair cells to the central auditory system, and cause significant hearing loss. Herein, a new form of bioactive hydrogel incorporating topological graphene oxide (GO) and TEMPO-oxidized bacterial cellulose (GO/TOBC hydrogel) was developed to provide a favorable microenvironment for SGN neurite outgrowth. As the network structure of lamellar interspersed fiber cross-linked by GO/TOBC hydrogels well simulated the structure and morphology of ECM, with the controllable hydrophilic property and appropriate Young's modulus well met those requirements of SGNs microenvironment, the GO/TOBC hybrid matrix exhibited great potential to promote the growth of SGNs. The quantitative real-time PCR result confirmed that the GO/TOBC hydrogel can significantly accelerate the development of growth cones and filopodia, by increasing the mRNA expression levels of diap3, fscn2, and integrin β1. These results suggest that GO/TOBC hydrogel scaffolds have the potential to be used to construct biomimetic nerve grafts for repairing or replacing nerve defects.

A Novel Highly Conductive, Transparent, and Strong Pure-Cellulose Film from TEMPO-Oxidized Bacterial Cellulose by Increasing Sonication Power.

Developing a conductive cellulose film without any metal compounds remains challenging, though in great demand. However, cellulose film prepared from bacterial cellulose (BC) powder without any metal compounds has poor tensile, physical, and electrical properties, thus limiting its application. Herein, this study aims to prepare and characterize an all-cellulose film from 2,2,6,6-Tetramethylpiperidin-1-yl)oxyl (TEMPO)-oxidized bacterial cellulose (TOBC) powders without adding metal compounds and treated by ultrasonication. TOBC powders are sonicated with various powers of 250, 500, and 750 W for 20 min without any other substance. It was proved that increasing the ultrasonication power level resulted in a significant improvement in the properties of the film. The ultrasonication of 750 W increased tensile strength by 85%, toughness by 308%, light transmittance by 542%, and electrical conductivity by 174% compared to the nonsonicated film. A light-emitting diode connected to a power source through this sonicated film was much brighter than that connected via a nonsonicated film. For the first time, this study reports the preparation of electrically conductive, transparent, strong, and bendable pure TOBC films by increasing ultrasonic power for environmentally friendly electronic devices application.

Multifunctional silk fibroin/PVA bio-nanocomposite films containing TEMPO-oxidized bacterial cellulose nanofibers and silver nanoparticles

Multifunctional silk fibroin/PVA bio-nanocomposite films containing TEMPO-oxidized bacterial cellulose nanofibers and silver nanoparticles

Mesoscopic confined ionic thermoelectric materials with excellent ionic conductivity for waste heat harvesting

Harvest energy from ubiquitous low-grade waste heat with thermoelectric (TE) materials is a prospective and crucial strategy in sustainable development. High-performance ionic thermoelectric (ITE) materials with flexible, low-cost, mass productive and biodegradable features are in high demand. Herein, a novel, flexible and high-performance ITE material (carboxyl-functionalized bacterial cellulose-based ionogels, CBCIGs) based on biofriendly 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized bacterial cellulose (TOBC) and “green” solvent (ionic liquid, 1-ethyl-3-methylimidazolium dicyanamide, [EMIm][DCA]) is reported. The as-fabricated CBCIG exhibits a high tensile strength, skin-like stretchability, excellent adhesion and biodegradability. The ionogels were designed to manipulate the confinement of ILs within the functionalized natural biopolymer, aiming to improve the electric conductivity as the ionic TE materials. The proposed CBCIG with 99.52 wt% [EMIm][DCA] exhibits a high ionic conductivity of 79 mS cm−1. The maximum Seebeck coefficient is 11.55 mV K−1 observed on CBCIGs-90 wt%. The employment of the CBCIGs as a flexible ionic thermoelectric capacitor (ITEC) device for thermoelectric conversion is also demonstrated. We expect that the development of the flexible ITE materials will provide an effective solution for utilizing low-grade waste heat for flexible wearable self-powered devices.

Improvement of O/W emulsion performance by adjusting the interaction between gelatin and bacterial cellulose nanofibrils

This study was designed to improve the stability of medium internal phase emulsion by adjusting the electrostatic interaction between gelatin (GLT) and TEMPO-oxidized bacterial cellulose nanofibrils (TOBC). The influences of polysaccharide-protein ratio (1:10, 1:5, and 1:2.5) and pH (3.0, 4.7, 7.0, and 11.0) on the emulsion properties were investigated. The droplet size of TOBC/GLT-stabilized emulsion was increased with the TOBC proportion increasing at pH 3.0–11.0. Additionally, emulsion had a larger droplet size at pH 4.7 (the electrical equivalence point pH of mixtures). However, the addition of TOBC significantly improved the emulsion stability. The emulsions prepared with TOBC/GLT mixtures (mixing ratio of 1:2.5) at pH 3.0–7.0 were stable without creaming during the storage. It was because the formation of nanofibrils network impeded the droplet mobility, and the emulsion viscosity and viscoelastic modulus were increased with the addition of TOBC. These findings were meaningful to modulate the physical properties of emulsions.

Development of intelligent/active food packaging film based on TEMPO-oxidized bacterial cellulose containing thymol and anthocyanin-rich purple potato extract for shelf life extension of shrimp

An intelligent and active film was developed based on 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized bacterial cellulose (TOBC) containing thymol (THY) and anthocyanin-rich purple potato extract (ANT). The microstructure, thermal stability, water vapor permeability, mechanical property and UV protection performance of TOBC-based films were evaluated. Scanning Electron Microscopy (SEM) and Atomic Force Microscope (AFM) results show the additions of THY and ANT bring about the uneven distribution of TOBC fibers with slightly increased surface roughness. Meanwhile, the introduction of THY and ANT could increase the thermal stability, UV protection and water vapor barrier property of TOBC with slightly decreased tensile strength. The prepared ANT exhibits a pH-sensitive activity, and it endows the fabricated TOBC/THY/ANT film with colorimetric response ability to volatile ammonia. TOBC/THY/ANT film also exhibits good antibacterial and antioxidant activities. Particular finding is that TOBC/THY/ANT film possesses simultaneously freshness real-time monitoring and good shrimp preservation abilities. The antioxidant, antibacterial and color response performances of TOBC/THY/ANT film were measured for three cycles in order to prove its recycling ability. These unique features of TOBC/THY/ANT film demonstrate the potential in commercial shrimp packaging with freshness real-time monitoring.

TEMPO-Oxidized Bacterial Cellulose Nanofibers/Graphene Oxide Fibers for Osmotic Energy Conversion.

The large osmotic energy between river water and seawater is an inexhaustible blue energy source; however, the complicated manufacturing methods used for ion-exchange devices hinder the development of reverse electrodialysis (RED). Here, we use a wet-spinning method to continuously spin meter-scale 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized bacterial cellulose (TOBC) nanofiber filaments, which are then used to construct nanochannels for osmotic energy conversion. These are then used to build a nacre-like structure by adding graphene oxide (GO), which provides narrow nanochannels in one-dimensional and two-dimensional nanofluid systems for rapid ion transport. With a 50-fold concentration gradient, the nanochannels in the fibers generate electricity of 0.35 W m-2, with an ionic mobility of 0.94 and an energy conversion efficiency of 38%. The assembly of GO and TOBC results in a high power density of 0.53 W m-2 using artificial seawater and river water. The RED device fabricated from TOBC/GO fibers maintains a stable power density for 15 days. This research proposes a simple method to reduce the size of nanochannels to improve the ionic conductivity, ionic selectivity, and power density of cellulose-based nanofibers to increase the possibility of their application for the conversion of osmotic energy to electrical energy.

Stability, Viscosity, and Tribology Properties of Polyol Ester Oil-Based Biolubricant Filled with TEMPO-Oxidized Bacterial Cellulose Nanofiber

This research is aimed at studying the stability and tribology properties of the polyol ester oil- (POE-) based biolubricant mixed with various filler loadings from microparticle of TEMPO-oxidized bacterial cellulose (NDCt) as an additive and sorbitan monostearate (Span 60) as a surfactant. Morphology, rheology, and tribology tests were conducted. The addition of NDCt and Span 60 to pure POE as a base fluid showed elevated viscosity, lower value of coefficient friction (COF), and a remarkable decrease in the wear rate (WR). The presence of 0.6 wt% NDCt and 1.8 wt% Span 60 in POE (N2S4) decreased the COF value by 79% in comparison to POE. At room temperature, this N2S4 biolubricant sample showed a higher thermal conductivity by 4% and lower WR value by 49% compared to POE. This study introduced the preparation of the ecofriendly biolubricant filled with NDCt improving the tribology properties remarkably.

Permeation of Silver Sulfadiazine Into TEMPO-Oxidized Bacterial Cellulose as an Antibacterial Agent.

Surface oxidation of bacterial cellulose (BC) was done with the TEMPO-mediated oxidation mechanism system. After that, TEMPO-oxidized bacterial cellulose (TOBC) was impregnated with silver sulfadiazine (AgSD) to prepare nanocomposite membranes. Fourier transform infrared spectroscopy (FTIR) was carried out to determine the existence of aldehyde groups on BC nanofibers and X-ray diffraction (XRD) demonstrated the degree of crystallinity. FESEM analysis revealed the impregnation of AgSD nanoparticles at TOBC nanocomposites with the average diameter size ranging from 11 nm to 17.5 nm. The sample OBCS3 showed higher antibacterial activity against Staphylococcus aureus, Pseudomonas aeruginosa, and Escherichia coli by the disc diffusion method. The results showed AgSD content, dependent antibacterial activity against all tested bacteria, and degree of crystallinity increases with TOBC and AgSD. The main advantage of the applications of TEMPO-mediated oxidation to BC nanofibers is that the crystallinity of BC nanofibers is unchanged and increased after the oxidation. Also enhanced the reactivity of BC as it is one of the most promising method for cellulose fabrication and functionalization. We believe that the novel composite membrane could be a potential candidate for biomedical applications like wound dressing, BC scaffold, and tissue engineering.

Production of Bacterial Cellulose Aerogels With Improved Physico-Mechanical Properties and Antibacterial Effect.

Aerogels have gained significant interest in recent decades because of their unique properties such as high porosity, low density, high surface area, and excellent heat and noise insulation. However, their high cost and low mechanical strength limit their practical application. We developed appropriate conditions to produce aerogels with controlled density, high mechanical strength, and thermal characteristics from bacterial cellulose (BC) synthesized by the strain Komagataeibacter sucrofermentans H-110. Aerogels produced using TEMPO oxidized BC (OBC) exhibited high mechanical strength and lower shrinkage than those from native bacterial cellulose (NBC). Compared to the NBC, the use of TEMPO-oxidized BC with oxidation degrees (OD) of 1.44 and 3.04% led to the reduction of shrinkage of the aerogels from 41.02 to 17.08%. The strength of the aerogel produced from the TEMPO-oxidized BC with an oxidation degree of 1.44% was twice that of the aerogel produced from NBC. The addition of Mg2+ at concentrations of 20 and 40 mM during the preparation of the aerogels increased the strength of the aerogels by 4.9 times. The combined use of TEMPO-oxidized BC and Mg2+ allowed pore size reduction from 1,375 to 197.4 μm on the outer part of the aerogels, thereby decreasing the thermal conductivity coefficient from 0.036 to 0.0176 W/(m•K). Furthermore, novel biocomposites prepared from the aerogels based on NBC and OBC and sodium fusidate, which have high antibiotic activity against Staphylococcus aureus, were obtained. Owing to their antibacterial properties, these aerogels can be used as functional biomaterials in a wide range of applications such as in tissue engineering and fabrication of wound dressing materials.

TEMPO-oxidized cellulose nanofibril film from nano-structured bacterial cellulose derived from the recently developed thermotolerant Komagataeibacter xylinus C30 and Komagataeibacter oboediens R37–9 strains

Bacterial cellulose (BC), prepared from two recently developed thermotolerant bacterial strains (Komagataeibacter xylinus C30 and Komagataeibacter oboediens R37–9), were used as a raw material to synthesize nanofibril films. Field-emission scanning electron microscope (FE-SEM) observations confirmed the ultrafine nano-structure of BC pellicle (BCP) with average fibril widths between 50 and 60 nm. The BC was directly oxidized in a TEMPO/NaBr/NaClO system at pH of 10 for 2 h. TEMPO-oxidized bacterial cellulose nanofibrils (TOBCN) were obtained by a mild mechanical treatment and the TOBCN films were prepared through heat-drying. The oxidation yielded a recovery ratio between 70 and 80% by weight with an increase in the carboxylate content of 0.9–1.0 mmol g −1. Nanofibrillation yields were more than 90% and the resulting high aspect ratio TOBCNs were ~6 nm in average width with >800 nm in lengths, when observed under transmission electron microscope (TEM). TOBCN film of K. xylinus C30 exhibited high transparency (79%), tensile strength (142 MPa), Young's modulus (7.13 GPa), elongation around failure (3.89%), and work of fracture (2.29 MJ m−3), when compared to the TOBCN films of K. oboediens R37–9 at 23 °C and 50% RH. Coefficients of thermal expansion of both the TOBCN films were low at around 6 ppm K−1.

A Semi-Dissolving Microneedle Patch Incorporating TEMPO-Oxidized Bacterial Cellulose Nanofibers for Enhanced Transdermal Delivery.

Although dissolving microneedles have garnered considerable attention as transdermal delivery tools, insufficient drug loading remains a challenge owing to their small dimension. Herein, we report a one-step process of synthesizing semi-dissolving microneedle (SDMN) patches that enable effective transdermal drug delivery without loading drugs themselves by introducing TEMPO-oxidized bacterial cellulose nanofibers (TOBCNs), which are well dispersed, while retaining their unique properties in the aqueous phase. The SDMN patch fabricated by the micro-molding of a TOBCN/hydrophilic biopolymer mixture had a two-layer structure comprising a water-soluble needle layer and a TOBCN-containing insoluble backing layer. Moreover, the SDMN patch, which had a hole in the backing layer where TOBCNs are distributed uniformly, could offer novel advantages for the delivery of large quantities of active ingredients. In vitro permeation analysis confirmed that TOBCNs with high water absorption capacity could serve as drug reservoirs. Upon SDMN insertion and the application of drug aqueous solution through the drug inlet hole, the TOBCNs rapidly absorbed the solution and supplied it to the needle layer. Simultaneously, the needle layer dissolved in body fluids and the drug solution to form micro-channels, which enabled the delivery of larger quantities of drugs to the skin compared to that enabled by solution application alone.