Search Results (58)

Dopamine is a major catecholamine neurotransmitter that plays an essential role in the functioning of the human central nervous system. Imbalances in dopamine levels are associated with neurological disorders and depression. Thus, measuring the concentration of DA in human body fluids is significantly important. In this work, TEMPO-oxidized cellulose nanofibrils (TOCNFs) extracted from marram grass (Ammophilia arenaria), harvested in the central western part of Tunisia, were utilized to modify disposable screen-printed carbon electrodes (SPCEs) for the sensitive detection of dopamine in biological fluids. Differential pulse voltammetry (DPV) measurements displayed a sensitivity of 7.92 µA/µM and a detection limit of 10 nM. The disposable TOCNF-modified SPCE presents a charge transfer coefficient, α, comparable to that of a TOCNF/graphene/AgNP composite-modified GCE. Moreover, it exhibits good repeatability (RSD = 1.9%), good reproducibility (RSD = 2.3%), and appreciable storage stability (91% of its initial response after 3 weeks). The prepared disposable sensor showed satisfactory recovery of dopamine in human urine samples. Full article

UiO-66-NH₂ is a metal–organic framework (MOF) with open metal sites, making it a promising candidate for adsorption and catalysis. However, the powdery texture of MOFs and the use of toxic solvents during synthesis limit their application. A novel solution to this issue is to create a layered porous composite by encasing the MOF within a flexible and structurally robust aerogel substrate using safe, eco-friendly, and green solvents such as ethanol. The fibrous MOF aerogels, characterized by a desirable macroscopic shape of cylindrical block and hierarchical porosity, were synthesized by two approaches: in situ growth of amine-functionalized UiO-66-NH₂ crystals on a TEMPO-oxidized cellulose nanofiber (TOCNF) and ex situ crosslinking of UiO-66-NH₂ crystals onto a TOCNF network to form UiO-66-NH₂/TOCNF. The incorporation of MOF into the cellulose nanofibrils via the in situ method reduces their aggregation potential, alters the nucleation/growth balance to produce smaller MOF crystals, and enhances mechanical flexibility, as evidenced by SEM images. The three adsorbents, including UiO-66-NH₂, ex situ UiO-66-NH₂/TOCNF, and in situ UiO-66-NH₂/TOCNF, were synthesized and used in this study. The effects of pH, time, temperature, and initial concentration were studied. A maximum adsorption capacity (Qmax) of 549.45 mg/g for Congo Red (CR) and 171.23 mg/g for Orange II (ORII) was observed at pH 6, using 10 mg of in situ UiO-66-NH₂/TOCNF at 40 °C with a contact time of 75 min for CR and 2 h for ORII. The adsorption of both dyes primarily occurs through monolayer chemisorption on the in situ UiO-66-NH₂/TOCNF. The main removal mechanisms were hydrogen bonding and surface complexation. The noteworthy adsorption capacity of in situ UiO-66-NH₂/TOCNF coupled with environment-friendly fabrication techniques indicates its potential applications on a large scale in real wastewater systems. Full article

New 3D printing aerogel materials are environmentally friendly and could be used in environmental protection and biomedical fields. There is significant research interest in 3D printing cellulose-based aerogels since cellulose materials are biocompatible and are abundant in nature. The gel-like nature of the cellulose water suspension is suitable for 3D printing; however, the complexity and resolution of the geometry of aerogels are quite limited, mainly due to the inks’ low viscosity that fails to maintain the integrity of the shape after printing. To address this limitation, a carefully optimized formulation incorporating three key ingredients, i.e., nanofibrils (TEMPO-CNFs), 2,2,6,6-tetramethyl-1-piperidinyloxy modified cellulose nanocrystals (TEMPO-CNC), and sodium carboxymethyl cellulose (CMC), is utilized to enhance the viscosity and structural stability of the ink. This combination of cellulose derivatives utilizes the electrostatic repulsive forces between the negatively charged components to form a stable and uniformly distributed suspension of cellulose materials. Our ink formulations improve printability and shape retention during 3D printing and are optimal for DIW printing. We print by employing an all cellulose-based composite ink using a modified direct ink writing (DIW) 3D printing method, plus an in situ freezing stage to form a layer-by-layer structure, and then follow a freeze-drying process to obtain the well-aligned aerogels. We have investigated the rheological properties of the ink formulation by varying the concentration of these three cellulose materials. The obtained aerogels exhibit highly ordered microstructures in which the micropores are well-aligned along the freezing direction. This study demonstrates a strategy for overcoming the challenges of 3D printing cellulose-based aerogels by formulating a stable composite ink, optimizing its rheological properties, and employing a modified DIW printing process with in situ freezing, resulting in highly ordered, structurally robust aerogels with aligned microporous architectures. Full article

Green bioprinting, from the context of merging 3D bioprinting with microalgae cell organization, holds promise for industrial-scale optimization. This study employs spectrophotometric analysis to explore post-bioprinting cell growth density variation within hybrid hydrogel biomaterial scaffolds. Three hydrogel biomaterials—Alginic acid sodium salt (ALGINATE), Nanofibrillated Cellulose (NFC)—TEMPO, and CarboxyMethyl Cellulose (CMC)—are chosen for their scaffolding capabilities. Bioink development and analysis of their impact on cell proliferation and morphology are conducted. Chlorella microalgae cell growth within hydrogel compositions is probed using absorbance measurements, with additional assessment of shear thinning properties. Notably, NFC exhibits reduced shear thinning compared to CMC. Results reveal that while mono-hydrogel substrates with pronounced adhesion inhibit Chlorella cell proliferation, alginate fosters increased cell concentration alongside a slight viscosity rise. Full article

This study investigates the enhancement of biomass slurry processability through the addition of rheological modifiers, focusing on carboxymethyl cellulose (CMC) and TEMPO-mediated oxidized cellulose nanofibrils (TCNF). Three sets of experiments were conducted to assess the effects of these additives on slurry processing and fermentation. Initial experiments evaluated the slurry extrudability, concluding that TCNF aids extrusion similarly to CMC. Subsequent experiments explored slurry viscosity reduction mechanisms, revealing that while CMC significantly reduced the viscosity, TCNF’s impact is negligible. Additionally, TCNF performed comparably to CMC in water retention tests across different conditions, which suggests that TCNF have potential as an effective additive for maintaining slurry fluidity at high solid concentrations through enhanced water retention. Lastly, both additives were investigated to ensure that they did not impact hydrolyzed biomass fermentation. The findings suggest that TCNF’s mechanisms differ from those of traditional water-soluble polymers like CMC, offering insights into novel approaches to improve the biomass processing efficiency and subsequent fermentation. Full article

Cellulose nanofibrils (CNFs) are particles with a high aspect ratio. Typically, chemically pre-treated CNFs (containing anionic or cationic charged groups) consist of long fibrils (up to 2 μm) with very low thickness (less than 10 nm). Derived from their high aspect ratio, CNFs form strong hydrogels with high elasticity at low concentrations. Thus, CNF suspensions appear as an interesting rheology modifier to be applied in cosmetics, paints, foods, and as a mineral suspending agent, among other applications. The high viscosity results from the strong 3D fibril network, which is related to the good fibrillation of the material, allowing the nanofibrils to overlap. The overlap concentration (c*) was found to vary from ca. 0.13 to ca. 0.60 wt.% depending on the type and intensity of the pre-treatment applied during the preparation of the CNFs. The results confirm the higher tendency for the fibres treated with (3-chloro-2-hydroxypropyl) trimethylammonium chloride (CHPTAC) and 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) to form a 3D network, resulting in the lowest c*. For the TEMPO-oxidised CNF suspensions, it was also found that aggregation is improved at acidic pH conditions due to lower charge repulsion among fibrils, leading to an increase in the suspension viscosity as well as higher apparent yield stresses. TEMPO CNF suspensions with a low content of carboxylic groups tend to precipitate at moderately acidic pH values. Full article

Red ginseng extract is one of the most widely used herbal medicines to prevent and cure various diseases. Among the processed products derived from red ginseng, the water-insoluble part as red ginseng residual (RGR) becomes waste, even though it contains important ingredients. TEMPO-oxidation (TO) can be used as a pre-treatment with different degrees of oxidation (DO) (0 to 0.4) in red ginseng residual (RGR-TO) by introducing chemical oxidation and high-pressure homogenizer (HPH) as a nanofibrillation process. ¹H NMR was used to determine the carbohydrate composition and calculate DO, size was examined using a nanoparticle analyzer, and the zeta potential was used to determine surface charge density. RGR-TO with different concentrations had different compositions; glucose and uronic acid were the main ingredients. All treated RGR-TO showed higher oxidant levels than the untreated counterpart (RGR-TO 0). As the oxidant levels increased, the zeta potential and uronic acid increased, but the size of the nanofibril from RGR-TO decreased. The results of this study showed that TEMPO-oxidation pretreatment was effective in producing RGR cellulose nanofibril (CNF) with a variety of properties by adjusting the level of oxidation pretreatment and the number of HPH passes. Full article

Biodegradable mulching films are a very attractive solution to agronomical practices intended to achieve more successful crop results. And, in this context, the employment of agricultural and industrial food residues as starting material for their production is an alternative with economic and environmental advantages. This work reports the preparation of bilayer films having two different wettability characteristics from three bio-derived biopolymers: TEMPO-oxidized cellulose nanofibers isolated from infused Yerba Mate residues, Chitosan and Polylactic acid. The infused Yerba Mate residues, the isolated and oxidized cellulose nanofibers, and the films were characterized. Nanofibrillation yield, optical transmittance, cationic demand, carboxyl content, intrinsic viscosity, degree of polymerization, specific surface area and length were studied for the (ligno)cellulose nanofibers. Textural and chemical analysis, thermal and mechanical properties studies, as well as water and light interactions were included in the characterization of the films. The bilayer films are promising materials to be used as mulching films. Full article

Regioselective C6 and C2,C3 carboxylated cellulose nanofibrils (CNFs) have been robustly generated from dissolving pulp, a readily available source of unmodified cellulose, via stoichiometrically optimized 2,2,6,6-tetramethylpyperidine-1-oxyl (TEMPO)-mediated and sequential sodium periodate-sodium chlorite (PC) oxidation coupled with high-speed blending. Both regioselectively optimized carboxylated CNF series possess the widest ranges of comparable charges (0.72–1.48 mmol/g for T-CNFs vs. 0.72–1.10 mmol/g for PC-CNFs), but similar ranges of thickness (1.3–2.4 nm for T-CNF, 1.8–2.7 nm PC-CNF), widths (4.6–6.6 nm T-CNF, 5.5–5.9 nm PC-CNF), and lengths (254–481 nm T-CNF, 247–442 nm PC-CNF). TEMPO-mediated oxidation is milder and one-pot, thus more time and process efficient, whereas the sequential periodate–chlorite oxidation produces C2,C3 dialdehyde intermediates that are amenable to further chemical functionalization or post-reactions. These two well-characterized regioselectively carboxylated CNF series represent coherent cellulose nanomaterial models from a single woody source and have served as references for their safety study toward the development of a safer-by-design substance evaluation tool. Full article

Nanofibrillated cellulose was extracted from potato peel waste using a fast and green method with a simple process. To extract cellulose and eliminate non-cellulosic constituents, alkaline and hydrogen peroxide treatments were performed under microwave irradiation. The nanofibrillated cellulose was extracted from purified cellulose via TEMPO oxidation followed by ultrasonication. The TEM, FTIR, XRD, and TGA experiments were used to evaluate the structural, crystalline, and thermal properties of cellulose fiber and nanofiber. The chemical and FTIR analysis of bleached fibers indicates that almost all non-cellulosic components of biomass have been eliminated. The diameter of the extracted nanofibers is in the range of 4 to 22 nm. In terms of crystallinity, extracted nanocellulose had 70% crystallinity, compared to 17% for unprocessed lignocellulose fibers, which makes it an excellent choice for use as a reinforcement phase in biobased composites. Thermogravimetric analysis reveals that cellulose nanofibers are less thermally stable than potato peel pure cellulose, but it has a higher char content (28%) than pure cellulose (6%), which signifies that the carboxylate functionality acts as a flame retardant. The comparison between cellulose derived from microwave and conventional extraction methods confirmed that their impact on the removal of non-cellulosic materials is nearly identical. Full article

Nanocellulose is an emerging green, biodegradable and biocompatible nanomaterial with negligible toxicities. In this study, a carboxylated nanocellulose (i.e., 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO)-oxidized cellulose nanofibril (TEMPO-CNF)) was prepared from corn stover and characterized by X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and differential scanning calorimetry (DSC)/thermogravimetric analysis (TGA). Corn stover-derived TEMPO-CNF was explored as an emulsion co-stabilizer together with Tween 80 for lemongrass essential oil-loaded emulsions. Droplet size, phase behavior and thermodynamic stability of oil-in-water emulsions stabilized by Tween 80 and TEMPO-CNF were investigated. The optimal nanoemulsion stabilized by this binary stabilizer could achieve a mean particle size of 19 nm, and it did not form any phase separation against centrifugal forces, freeze–thaw cycles and at least 30 days of room temperature storage. The nanoencapsulated essential oil had better inhibition activity against the mycelial growth of Aspergillus flavus than pure essential oil. Results from this study demonstrate the potential of using agricultural byproduct-derived nanomaterial as nanoemulsion stabilizers for essential oils with good emulsion thermodynamic stability as well as enhanced antifungal activities. Full article

The cost-effective implementation of nanofibrillated cellulose (CNF) at industrial scale requires optimizing the quality of the nanofibers according to their final application. Therefore, a portfolio of CNFs with different qualities is necessary, as well as further knowledge about how to obtain each of the main qualities. This paper presents the influence of various production techniques on the morphological characteristics and properties of CNFs produced from a mixture of recycled fibers. Five different pretreatments have been investigated: a mechanical pretreatment (PFI refining), two enzymatic hydrolysis strategies, and TEMPO-mediated oxidation under two different NaClO concentrations. For each pretreatment, five high-pressure homogenization (HPH) conditions have been considered. Our results show that the pretreatment determines the yield and the potential of HPH to enhance fibrillation and, therefore, the final CNF properties. These results enable one to select the most effective production method with the highest yield of produced CNFs from recovered paper for the desired CNF quality in diverse applications. Full article

To design a new system of novel TEMPO-oxidized cellulose nanofibrils (TOCNs)/graphene oxide (GO) composite, 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-mediated oxidation was utilized. For the better dispersion of GO into the matrix of nanofibrillated cellulose (NFC), a unique process combining high-intensity homogenization and ultrasonication was adopted with varying degrees of oxidation and GO percent loadings (0.4 to 2.0 wt%). Despite the presence of carboxylate groups and GO, the X-ray diffraction test showed that the crystallinity of the bio-nanocomposite was not altered. In contrast, scanning electron microscopy showed a significant morphological difference in their layers. The thermal stability of the TOCN/GO composite shifted to a lower temperature upon oxidation, and dynamic mechanical analysis signified strong intermolecular interactions with the improvement in Young’s storage modulus and tensile strength. Fourier transform infrared spectroscopy was employed to observe the hydrogen bonds between GO and the cellulosic polymer matrix. The oxygen permeability of the TOCN/GO composite decreased, while the water vapor permeability was not significantly affected by the reinforcement with GO. Still, oxidation enhanced the barrier properties. Ultimately, the newly fabricated TOCN/GO composite through high-intensity homogenization and ultrasonification can be utilized in a wide range of life science applications, such as the biomaterial, food, packaging, and medical industries. Full article

Flexible calcium carbonate (FCC) was developed as a functional papermaking filler for high loaded paper, which was a fiber-like shaped calcium carbonate produced from the in situ carbonation process on the cellulose micro-or nanofibril surface. Chitin is the second most abundant renewable material after cellulose. In this study, a chitin microfibril was utilized as the fibril core for making the FCC. Cellulose fibrils for the preparation of FCC were obtained by fibrillation of the TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical) treated wood fibers. The chitin fibril was obtained from the β-chitin from the born of squid fibrillated in water by grinding. Both fibrils were mixed with calcium oxide and underwent a carbonation process by the addition of carbon dioxide, thus the calcium carbonate attached on the fibrils to make FCC. When used in papermaking, both the FCC from chitin and cellulose gave a much higher bulk and tensile strength simultaneously than the conventional papermaking filler of ground calcium carbonate, while maintaining the other essential properties of paper. The FCC from chitin caused an even higher bulk and higher tensile strength than those of the FCC from cellulose in paper materials. Furthermore, the simple preparation method of the chitin FCC in comparison with the cellulose FCC may enable a reduction in the use of wood fibers, process energy, and the production cost of paper materials. Full article

Agricultural byproducts such as corn stover are widely available sources for preparation of nanocellulose, which is an emerging green chemical with versatile applications. In this study, corn stover-derived nanocellulose was prepared via bleaching, alkaline treatment, 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) oxidation, and ultrasonication. The as-prepared TEMPO-oxidized cellulose nanofibril (TEMPO-CNF) was characterized by transmission electron microscopy, UV-Vis spectrophotometry, rheometry, and zeta potential measurement. Droplet size, phase behavior, and thermodynamic stability of TEMPO-CNF stabilized oil-in-water emulsions were investigated. Results show that TEMPO-CNF with a width of 4 nm, length of 353 nm, and surface charge of 1.48 mmol/g COO^- can be prepared from corn stover. In addition, TEMPO-CNF can be used as an emulsion stabilizer for lemongrass essential oil loaded oil-in-water emulsion. This study is among the first to report that TEMPO-CNF improved the freeze-thaw stability of oil-in-water emulsions stabilized by small molecular weight surfactants (e.g., Tween 80). Full article