TEMPO-mediated surface oxidation of cellulose whiskers

Cellulose whiskers resulting from HCl acid hydrolysis of tunicin were subjected to TEMPO-mediated oxidation under various conditions and the extent of the resulting oxidation was characterized by Fourier-transform infrared spectroscopy (FT-IR), conductimetry, X-Ray diffraction analysis and transmission electron microscopy (TEM). With degree of oxidation of up to 0.1 the samples kept their initial morphological integrity and native crystallinity, but at their surface the hydroxymethyl groups were selectively converted to carboxylic groups, thus imparting a negative surface charge to the whiskers. When dispersed in water these oxidized whiskers did not flocculate and their suspensions appeared birefringent when viewed between cross polarizers, thus indicating a liquid crystalline behavior.     

TEMPO-mediated oxidation of bacterial cellulose in a bromide-free system

A partially C6-carboxylated bacterial cellulose (BC) with a high carboxylate content was prepared in a bromide-free system by using 2,2,6,6-tetramethylpyperidine-1-oxyl (TEMPO) as a catalyst. ART-FTIR, X-ray diffraction, solid ¹³C-NMR, TEM analysis, and reaction kinetics measurements were performed to investigate the oxidation reaction of BC. Results show that C6 carboxylate was formed selectively on the microfiber surface without disrupting its highly ordered nanocrystalline structure. Given the extremely low accessibility of hydroxyl groups in d-anhydroglucopyranose units, the reaction can be described by second-order kinetics with very low reaction rate constants. pH exhibited a significant influence on the oxidation of BC and a higher activity at C6 was observed in a neutral medium.     

Kinetic study on TEMPO-mediated selective oxidation of regenerated cellulose

The kinetics of the TEMPO-mediated oxidation of regenerated celluloses has been studied. It is revealed that the oxidation reaction of the regenerated celluloses by the 2,2,6,6-tetramethyl-piperidine-1-oxyl radical (TEMPO)–NaBr–NaOCl system can be approximately described by first-order kinetics with respect to substrate. In the concentration range used the rate constant k is directly proportional to the concentration of TEMPO, while it is proportional to the concentration of NaBr in a relatively lower range and tends to level off at higher concentration. The effect of temperature on the rate constant can be well described by the Arrhenius equation, the apparent activation energy measured is about 66.2 kJ/mol. The effect of the pH of the reaction solution, the crystallinity and morphology of the substrates on the oxidation rate is also discussed.     

TEMPO-mediated oxidation of microcrystalline cellulose: limiting factors for cellulose nanocrystal yield

Cellulose nanocrystal (CNC) production suffers, among other problems, from low yields. The focus of this study was to investigate the universal effect of charge density, centrifugation, and mechanical treatment as limiting causes of yield. Microcrystalline cellulose (MCC) was used as the starting material in order to eliminate the relatively arbitrary yield losses caused by the hydrolysis conditions. To disintegrate MCC into nanocrystals, high surface charge in the form of carboxylic groups was introduced by TEMPO-mediated oxidation, after which the material was mechanically treated, and separated into fine and coarse fractions. The fine fraction collected as supernatant after separation by centrifugation had a yield of 17–20% independent of the mechanical treatment method or time used. The particle sizes of these fractions did not significantly differ from each other, which raises questions on the efficiency of the mechanical treatment (sonication) and centrifugation in traditional CNC production. The results imply that radically new approaches in preparation are needed for truly meaningful increases in the CNC yield.     

TEMPO-mediated surface oxidation of cellulose nanocrystals (CNCs)

Cellulose nanocrystals were successfully oxidized with sodium hypochlorite using catalytic amounts of sodium bromide and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radical at pH 10 in water. Carboxylate groups were selectively introduced at the surface of the crystals up to a total acid content of 1200 mmol kg^?1 without damaging the integrity of the crystals. The final acid content can easily be tuned by varying the amount of oxidant introduced. The effect of temperature, the quantity of oxidant and co-catalyst on the reaction kinetics were studied. Several methods were used for the characterization of the oxidized material like field emission scanning electron microscopy, diffuse reflectance infrared spectroscopy and thermogravimetric analysis.     

Optimization of cellouronic acid synthesis by TEMPO-mediated oxidation of cellulose III from sugar beet pulp

Microfibrillated cellulose from purified sugar beet pulp was converted into cellulose III by immersion in liquid ammonia. When freed from ammonia, this product was oxidized in water at pH-10 using NaBr, NaOCl and 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) under various conditions and concentrations. The resulting water-soluble cellouronic acid—i.e. cellulose oxidized at the C6 position- was analyzed by high performance size exclusion chromatography (HPSEC) together with ¹³C NMR spectroscopy. The oxidation parameters, namely reaction time, temperature, NaBr and TEMPO concentrations were varied to determine the optimum reaction conditions. A low TEMPO concentration, a rather fast reaction time and the conducting of the oxidation at 0 °C were critical to obtain pure cellouronic acid in high yield, high purity and high DP.     

Characterization of cellulose nanofibrils prepared by direct TEMPO-mediated oxidation of hemp bast

Hemp bast (α-cellulose 79.4%, Klason lignin 4.9%) was directly oxidized by 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-mediated oxidation in water at pH 10 and room temperature for 2 h. The level of added NaClO in oxidation varied from 5 to 30 mmol/g (based on dry weight of hemp bast). Weight recovery ratios of the TEMPO-oxidized hemp bast celluloses were in the range of 81–91%, and their carboxylate contents increased up to 1.2 mmol/g with the increased NaClO addition level. The lignin contents decreased to 0.5–0.9% after oxidation, and the viscosity-average degrees of polymerization decreased from 1100 to 560 because of depolymerization during oxidation. Thus, direct TEMPO-mediated oxidation of hemp bast introduced a significant number of carboxylate groups and simultaneously achieved sufficient delignification. Small amounts of xylose, mannose, and rhamnose originating from hemicelluloses remained in the TEMPO-oxidized hemp bast samples prepared by oxidation with 5–20 mmol/g NaClO. However, oxidation with 30 mmol/g NaClO completely removed these hemicellulose-originating sugars, and produced almost pure TEMPO-oxidized cellulose. When TEMPO-oxidized hemp bast samples were mechanically disintegrated in water, their nanofibrillation yields were 58–65%. After removal of unfibrillated fractions by centrifugation, transparent dispersions showed birefringence when observed between cross-polarizers, while atomic force microscopy images showed near-individually dispersed nanofibril elements with widths of ~2 nm.     

SEC-MALS analysis of cellouronic acid prepared from regenerated cellulose by TEMPO-mediated oxidation

The 4-amino-2,2,6,6-tetramethylpiperidine-1-oxy radical (4-amino-TEMPO)-mediated oxidation was applied to regenerated cellulose, and the obtained cellouronic acid was analyzed by size-exclusion chromatography attached with a multi-angle laser light scattering detector (SEC-MALS). Although the cellouronic acid filtered with the usual 0.1 μm membrane gave a bimodal SEC-elution pattern, the high-molecular-mass fraction was removed by micro filtration of the cellouronic acid solution with a 0.02 μm membrane. It is likely, therefore, that some colloidal particles formed from regenerated cellulose by the TEMPO-mediated oxidation are present as incompletely oxidized residues in the cellouronic acid sample and behave as the high-molecular-mass fraction in the SEC elution pattern. Then, the SEC-MALS analysis was applied to the 0.02 μm membrane-filtered cellouronic acid, and the accurate DPw value of 36 was obtained for cellouronic acid. This DPw value was far lower than that of carboxymethyl cellulose, hydroxypropyl cellulose or alginic acid, resulting from significant depolymerization of cellulose chains during the TEMPO-mediated oxidation. Because the value of DPw 36 for cellouronic acid is close to the leveling-off DP (about 40) of regenerated celluloses obtained by the dilute and heterogeneous acid hydrolysis, the DPw value of cellouronic acid must reflect the solid-state structure of the original regenerated cellulose used in the TEMPO-mediated oxidation.     

Water dispersion of cellulose II nanocrystals prepared by TEMPO-mediated oxidation of mercerized cellulose at pH 4.8

Mercerized wood cellulose was oxidized by 4-acetamide-TEMPO/NaClO/NaClO₂ system at 60 °C and pH 4.8 for 1–5 days. Mostly individual nanocrystals 4–7 nm in width and 100–200 nm in length were obtained by ultrasonication of the oxidized product in water. The nanocrystals had the cellulose II structure, and carboxylate contents of 2.0–2.4 mmol/g, indicating that these carboxylate groups were selectively formed on the cellulose II crystallite surfaces in mercerized cellulose. Moreover, the original wood cellulose and mercerized cellulose were acid-hydrolyzed, and then subjected to the TEMPO-mediated oxidation under the same conditions at pH 4.8 to prepare reference samples. TEM images, light transmittance and rheological properties of water dispersions showed that the nanocrystals prepared from mercerized cellulose by the TEMPO oxidation and sonication in water had the highest dispersibility of individual nanocrystals with less amounts of bundles in water, resulting from the highest carboxylate contents.     

Sonocatalysis of the TEMPO-mediated oxidation of glucosides

Ultrasound is shown to increase the rate of the TEMPO-mediated oxidation of methyl - -glucopyranoside or sucrose in the presence of stoichiometric amounts of sodium hypochlorite in basic aqueous medium. The reaction can then occur without the usually necessary sodium bromide, showing that ultrasound acts at the level of the formation of the nitrosonium ion, the active oxidizing species in the catalytic cycle.     

Depolymerization of cellouronic acid during TEMPO-mediated oxidation

The mechanism of partial depolymerization of cellouronic acid (-1,4-linked polyglucuronic acid sodium salt) during 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation of cellulose was studied by treating cellouronic acid with one reagent or a combination of TEMPO-NaBr-NaClO under various conditions. Although NaClO, NaBrO and an alkali at pH 11 brought about partial depolymerization of cellouronic acid, the use of these reagents themselves did not seem to be the primary reason for depolymerization. On the other hand, when all the reagents, i.e. TEMPO-NaBr-NaClO, were applied to cellouronic acid at pH 11, a remarkable decrease in weight-average degree of polymerization (DPw) from 430 to ca. 20 was observed within the initial 10 min. Probably hydroxyl radicals formed from NaBrO and TEMPO at pH 10–11 cause the depolymerization during the oxidation. Some radical scavengers were then used for the TEMPO-mediated oxidation of cellulose in order to suppress the depolymerization. Although the addition of crotonic acid under certain conditions gave cellouronic acid having higher DPw, none of the radical scavengers examined so far could completely prevent the depolymerization. When regenerated celluloses having higher DP were used as the starting materials, cellouronic acids having DPw of more than 1000 were obtained, although they still had large low-molecular-weight fractions.     

Reactivity of dissolving pulps modified by TEMPO-mediated oxidation

The reactivity of dissolving pulps towards derivatization or dissolution is a crucial quality parameter and is mainly determined by the accessibility of the hydroxyl groups. When dissolving pulps are produced from paper-grade pulps by cold caustic extraction (CCE), their reactivity is often inferior as compared to commercial prehydrolysis kraft dissolving pulps. It was hypothesized that pulp reactivity can be enhanced by the introduction of small amounts of substituents to facilitate interchain accessibility. In this study, CCE-treated Eucalyptus globulus kraft paper pulp was subjected to TEMPO-mediated oxidation to initiate partial oxidation of the C₆-hydroxyl groups to carboxyl groups. The effect of this pulp modification on the reactivity towards xanthation and the subsequent dissolution in diluted aqueous alkali solution (viscose process) as well as the dissolution in complexing and non-complexing solvents, respectively, was thoroughly examined. The results revealed that the oxidized pulps rich in C₆-carboxylate groups impeded the xanthation reaction obviously because of the reduced availability of hydroxyl groups. When N-methylmorpholine-N-oxide monohydrate was used as a direct solvent, a very high content of C₆-carboxylate groups was found to reduce the solubility of the pulp fibers as less hydrogen bonds can be formed with NMMO·H₂O. In the case of dissolution in the complexing solvent cupriethylenediamine, the dissolution mechanism of cellulose was not deteriorated by the high content of C₆-carboxylate groups. Instead, the oxidation procedure increased the hydrophilic character and the swelling capacity of the outer cell wall layers allowed homogeneous dissolution.     

Reinforcement of cellulose nanofibers in polyacrylamide gels

Cellulose nanofibers (CNFs) have emerged as a promising nanofiller for effective reinforcement of nanocomposites due to their excellent mechanical properties. In this study, CNFs were fabricated by a simple grinding method and used to strengthen polyacrylamide (PAM) gels through in situ free radical polymerization. The morphology, compression properties, and chemical structure of the prepared gels were investigated. The results showed that large amounts of nanofibers embedded inside the PAM matrix and formed network structure by increasing the CNF content. Significantly, PAM/CNF gel with 5 wt% CNF exhibited highly improved compression strength by 6.8-fold as compared to that of pure PAM gel. The FTIR analysis indicated that hydrogen bondings between CNF and PAM chains mainly contributed to the superior mechanical properties of the hybrid gels. In summary, this study provides a novel alternative approach for preparing tough composite gels by combing rigid CNF and soft polymer and extending the application of biomedical load-bearing gel materials such as artificial cartilage and other soft tissues.     

Antimicrobial activity of silver nanoparticles in situ growth on TEMPO-mediated oxidized bacterial cellulose

In order to improve the antimicrobial activity of bacterial cellulose (BC), the silver nanoparticles (Ag NPs) were in situ fabricated on the BC membranes, affording BC and Ag hybrid antimicrobial materials, BC + Ag, which possesses excellent antimicrobial performance. Typically, carboxyl groups were firstly introduced into BC by TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical)-mediated oxidation. Then, the carboxyl-functionalized BC was performed with ion-exchange reaction to change the sodium ions into Ag⁺ by immersing in AgNO₃ aqueous solution, generating Ag⁺ anchored BC. Finally, two types of distinct reductive reagents including NaBH₄ and sodium citrate were employed to transform Ag⁺ into Ag NPs to fabricate BC + Ag. The diameters of Ag NPs were determined to be 3.8 nm for NaBH₄-reduced BC + Ag, and 22.0 nm for sodium citrate-reduced one, respectively. The silver content of BC + Ag were determined to be 1.944 and 2.895 wt% for NaBH₄-reduced sample and sodium citrate-reduced one, respectively. Two types of BC + Ag both showed a slow and persistent Ag⁺ release profile, but the NaBH₄-reduced one released much more Ag⁺ than that of sodium citrate under the same measurement condition. In-depth antibacterial analysis via the disc diffusion and colony forming count method disclosed that BC + Ag exhibited strong bactericidal effects against both Escherichia coli and Staphylococcus aureus. And the antibacterial activity of NaBH₄-reduced BC + Ag was higher than the sodium citrate-reduced one. Overall, this study would further improve the antibacterial efficiency of BC + Ag.     

Effect of xylan in hardwood pulp on the reaction rate of TEMPO-mediated oxidation and the rheology of the final nanofibrillated cellulose gel

alkali-washed nanofibrillated cellulose (NFC) samples, obtained from hardwood kraft pulp, with different amounts of retained xylan were prepared to study the influence of xylan on the water-retention properties of NFC suspensions. In this study, NFC was produced using an oxoammonium-catalyzed oxidation reaction that converts the cellulosic substrate to a more highly oxidized material via the action of the nitroxide radical species 2,2,6,6-tetramethylpiperidine-1-oxyl. Reduction of the xylan content in NFC was achieved by cold alkali extraction of kraft pulp. The pulps were then oxidized to a set charge under constant chemical conditions, and the reaction time was determined. The xylan content of the feed pulp was found to have a large negative influence on the oxidation rate of the pulp, as the oxidation time shortened when xylan was removed, from 220 min (for 25.2 % xylan content) to 28 min (for 7.3 % xylan content). Following fibrillation by homogenization, the swelling of the NFC was determined by a two-point solute exclusion method. The distribution of hemicellulose over the fibril surface was observed by atomic force microscopy. Xylan was found to be distributed unevenly over the surface, and its presence increased the water immobilized within flocs of NFC, i.e., so-called network swelling. The swelling of the NFC had a large impact on its rheology and dewatering. Comparison of the morphological and swelling properties of the suspensions with their rheological and dynamic dewatering behavior showed that reducing the xylan content in NFC results in a weaker gel structure of the nanocellulose suspension. The results indicate that most of the water is held by the swollen structure by means of xylan particles trapped within the hemicellulose layer covering the fibril surface. Samples with high xylan content had high shear modulus and viscosity and were difficult to dewater.     

Energy requirements for the disintegration of cellulose fibers into cellulose nanofibers

Cellulose nanofibers have a bright future ahead as components of nano-engineered materials, as they are an abundant, renewable and sustainable resource with outstanding mechanical properties. However, before considering real-world applications, an efficient and energetically friendly production process needs to be developed that overcomes the extensive energy consumption of shear-based existing processes. This paper analyses how the charge content influences the mechanical energy that is needed to disintegrate a cellulose fiber. The introduction of charge groups (carboxylate) is achieved through periodate oxidation followed by chlorite oxidation reactions, carried out to different extents. Modified samples are then subjected to different levels of controlled mechanical energy and the yields of three different fractions, separated by size, are obtained. The process produces highly functionalized cellulose nanofibers based almost exclusively on chemical reactions, thus avoiding the use of intensive mechanical energy in the process and consequently reducing drastically the energy consumption.     

TEMPO-mediated oxidation of corncob holocellulose and its influences on paper properties

In this study, the agricultural by-products of corn production (corncobs) were ground into a powder form. Then, the powder was treated with sodium chlorite to remove the lignin, and the remaining holocellulose was optionally modified with 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)-mediated oxidation. The resulting product was examined using an elemental analysis, along with Fourier transform infrared spectroscopy (FTIR). The effects of the oxidation time and dosages of the TEMPO on the paper’s physical properties were investigated. The results indicated that the TEMPO-mediated oxidized corncob holocellulose had the ability to improve the properties of both paper and recycled paper. When 1.0% oxidized holocellulose was used, the resulting tensile index, burst index, and folding endurance were increased by 4.16%, 8.63%, and 50.71%, respectively, compared with the control paper. The SEM analysis indicated that the bonding between fibers was improved by adding oxidized corncob holocellulose. Compared with the control paper, it was determined that the proportion of mesopore within the fibers increased and the bonding of the C–O bonds increased in the paper with the oxidized corncob holocellulose. The results of this study may potentially provide guidance for the future high value-added application of corncobs as a paper strengthening agent.     

Preparation of cellulose nanofibers with hydrophobic surface characteristics

The aim of this study was to develop cellulose nanofibers with hydrophobic surface characteristics using chemical modification. Kenaf fibers were modified using acetic anhydride and cellulose nanofibers were isolated from the acetylated kenaf using mechanical isolation methods. Fourier transform infrared spectroscopy (FTIR) indicated acetylation of the hydroxyl groups of cellulose. The study of the dispersion demonstrated that acetylated cellulose nanofibers formed stable, well-dispersed suspensions in both acetone and ethanol. The contact angle measurements showed that the surface characteristics of nanofibers were changed from hydrophilic to more hydrophobic when acetylated. The microscopy study showed that the acetylation caused a swelling of the kenaf fiber cell wall and that the diameters of isolated nanofibers were between 5 and 50 nm. X-ray analysis showed that the acetylation process reduced the crystallinity of the fibers, whereas mechanical isolation increased it. The method used provides a novel processing route for producing cellulose nanofibers with hydrophobic surfaces.     

Toughness enhancement of cellulose nanocomposites by alkali treatment of the reinforcing cellulose nanofibers

Nanocomposites were produced with NaOH aqueous solution-treated microfibrillated cellulose (MFC) and phenolic resin, and the mechanical properties were compared with their microcomposite counterparts based on pulp fiber. Tensile tests showed that strong alkali-treated MFC nanocomposites with resin content around 20 wt.% achieved strain at fracture values two times higher than those of untreated MFC nanocomposites and five times higher than those of untreated pulp microcomposites. The improvement in work of fracture of alkali-treated MFC nanocomposites was attributed to the ductility of the nanofibers caused by transformations in the amorphous regions along the cellulose microfibrils.