Characterization of TEMPO-Oxidized Cellulose Nanofiber From Biowaste and Its Influence on Molecular Behavior of Fluorescent Rhodamine B Dye in Aqueous Suspensions.

Cellulose nanofiber (CNFs) obtained through TEMPO oxidation was structurally characterized using FT-IR (Fourier Transformed Infrared) and SEM (Scanning Electron Microscopy) spectroscopy. The molecular aggregation and spectroscopic properties of Rhodamine B (Rh-B) in CNFs suspension were investigated using molecular absorption and steady-state fluorescence spectroscopy techniques. The interaction between CNFs particles in the aqueous suspension and the cationic dye compound was examined in comparison to its behavior in deionized water. This interaction led to significant changes in the spectral features of Rh-B, resulting in an increase in the presence of H-dimer and H-aggregate in CNFs suspension. The H-type aggregates of Rh-B in CNFs suspensions were defined by the observation of a blue-shifted absorption band compared to that of the monomer. Even at diluted dye concentrations, the formation of Rh-B's H-aggregate was observed in CNFs suspension. The pronounced aggregation in suspensions originated from the strong interaction between negatively charged carboxylate ions and the dye. The aggregation behavior was discussed with deconvoluted absorption spectra. Fluorescence spectroscopy studies revealed a significant reduction in the fluorescence intensity of the dye in CNFs suspension due to H-aggregates. Furthermore, the presence of H-aggregates in the suspensions caused a decrease in the quantum yield of Rh-B compared to that in deionized water.

Fabrication of composite hydrogels by sonication-assisted assembly of okara cellulose nanofibers and chitosan: structure and properties.

BACKGROUND: Okara cellulose is a highly abundant, green, sustainable, and biodegradable polymer with many potential industrial applications. In this study, we fabricated composite hydrogels with okara cellulose nanofibers (CNFs) and chitosan (CH) by hydrating, sonicating, and heating them at 100 °C for 30 min, and then induced their assembly by cooling. The effects of okara CNF (with and without 2,2,6,6-tetramethylpiperidinyloxy (TEMPO) oxidation) and CH concentration on the structure and properties of the hydrogels was examined, including their microstructure, surface properties, rheological properties, and thermal stability. RESULTS: Our results indicate that there was an electrostatic attraction between the anionic okara CNF and cationic CH, which facilitated hydrogel formation. The surface, textural, rheological, and thermal stability properties were better for the composite hydrogels than for the single CH ones, as well as for the CNF that had undergone TEMPO oxidation. For the TC-CH hydrogels, the contact angle was 39.5°, the interfacial tension was 69.1 mN m-1 , and the surface tension was 1.44 mN m-1 . CONCLUSION: In this study, the novel hydrogels developed may be useful as a soft material in a range of applications in foods, supplements, health care products, cosmetics, and drugs. © 2023 Society of Chemical Industry.

ClO2-Mediated Oxidation of the TEMPO Radical: Fundamental Considerations of the Catalytic System for the Oxidation of Cellulose Fibers.

The reaction mechanism of ClO2-mediated TEMPO oxidation was investigated by EPR spectroscopy and UV-Vis spectroscopy in the context of an alternative TEMPO sequence for cellulose fiber oxidation. Without the presence of a cellulosic substrate, a reversibility between TEMPO and its oxidation product, TEMPO+, was displayed, with an effect of the pH and reagent molar ratios. The involvement of HOCl and Cl-, formed as byproducts in the oxidation mechanism, was also evidenced. Trapping HOCl partly inhibits the reaction, whereas adding methylglucoside, a cellulose model compound, inhibits the reversibility of the reaction to TEMPO.

Synthesis and Antioxidative Properties of 1,2,3,4-Tetrahydropyridine Derivatives with Different Substituents in 4-Position.

Natural products are an excellent source of inspiration for the development of new drugs. Among them, betalains have been extensively studied for their antioxidant properties and potential application as natural food dyes. Herein, we describe the seven-step synthesis of new betalamic acid analogs without carboxy groups in the 2- and 6-position with an overall yield of ~70%. The Folin-Ciocalteu assay was used to determine the antioxidant properties of protected intermediate 21. Additionally, the five-step synthesis of betalamic acid analog 35 with three ester moieties was performed. Using NMR techniques, the stability of the obtained compounds towards oxygen was analyzed.

The measurement of molecular interactions, structure and physical properties of okara cellulose composite hydrogels using different analytical methods.

BACKGROUND: Aiming to address the practical problems of a low utilization rate and the serious waste of soybean residue, novel composite hydrogels based on okara cellulose before and after 2,2,6,6-tetramethylpiperidine oxide (TEMPO) oxidation and high polymers of chitosan (CH), carrageenan (CA) or Arabic gum (AG) were prepared by a homogeneous mixture in ionic liquid. RESULTS: In the present study, composite hydrogels fabricated from okara cellulose and CH, CA or AG were prepared by dissolving them in an ionic liquid, followed by heating (100 °C, 3 h) and then soaking them in a 1:1 water-isopropanol solution. The composite hydrogels prepared from TEMPO oxidation-treated cellulose were physically cross-linked to CH, CA or AG. The results showed that the intramolecular hydrogen bonds in the amorphous regions of the cellulose were disrupted, whereas the intermolecular hydrogen bonds between the biopolymers were increased, which promoted the formation of composite gels with crystalline structures. The TEMPO treatment increased the gel strength. For example, for the cellulose/CA gels, the hardness, fracturability, springiness and cohesiveness values were 5.9-, 4.3-, 2.4- and 3.6-fold higher compared to the non-treated ones, respectively. The composite hydrogels exhibited good thermal stability, swelling properties and mechanical properties. These novel composite polysaccharide-based hydrogels may therefore have great potential in various food and non-food fields. CONCLUSION: In summary, the addition of polymers (CH, CA or AG) and TEMPO oxidized cellulose was suitable for increasing the swelling, textural properties, thermal stability and rheological properties of hydrogels, which provides new ideas and new methods for the preparation of bio-based composite hydrogels. © 2022 Society of Chemical Industry.

TEMPO-Oxidized Cellulose Beads as Potential pH-Responsive Carriers for Site-Specific Drug Delivery in the Gastrointestinal Tract.

The development of controlled drug delivery systems based on bio-renewable materials is an emerging strategy. In this work, a controlled drug delivery system based on mesoporous oxidized cellulose beads (OCBs) was successfully developed by a facile and green method. The introduction of the carboxyl groups mediated by the TEMPO(2,2,6,6-tetramethylpiperidine-1-oxyradical)/NaClO/NaClO2 system presents the pH-responsive ability to cellulose beads, which can retain the drug in beads at pH = 1.2 and release at pH = 7.0. The release rate can be controlled by simply adjusting the degree of oxidation to achieve drug release at different locations and periods. A higher degree of oxidation corresponds to a faster release rate, which is attributed to a higher degree of re-swelling and higher hydrophilicity of OCBs. The zero-order release kinetics of the model drugs from the OCBs suggested a constant drug release rate, which is conducive to maintaining blood drug concentration, reducing side effects and administration frequency. At the same time, the effects of different model drugs and different drug-loading solvents on the release behavior and the physical state of the drugs loaded in the beads were studied. In summary, the pH-responsive oxidized cellulose beads with good biocompatibility, low cost, and adjustable release rate have shown great potential in the field of controlled drug release.

Copper-Mediated Conversion of Complex Ethers to Esters: Enabling Biopolymer Depolymerisation under Mild Conditions.

Selective processing of the ß-O-4 unit in lignin is essential for the efficient depolymerisation of this biopolymer and therefore its successful integration into a biorefinery set-up. An approach is described in which this unit is modified to incorporate a carboxylic ester with the goal of enabling the use of mild depolymerisation conditions. Inspired by preliminary results using a Cu/TEMPO/O2 system, a protocol was developed that gave the desired ß-O-4-containing ester in high yield using certain dimeric model compounds. The optimised reaction conditions were then applied to an oligomeric lignin model system. Extensive 2D NMR analysis demonstrated that analogous chemistry could be achieved with the oligomeric substrate. Mild depolymerisation of the ester-containing oligomer delivered the expected aryl acid monomer.

Composite hydrogels formed from okara cellulose nanofibers and carrageenan: Fabrication and characterization.

Currently, there is great interest in converting edible agro-waste, such as okara from soybean production, into value-added products. For this study, we focus on fabricating composite hydrogels from okara cellulose nanofibers (CNFs) and carrageenan (CA). We also examined the effects of TEMPO oxidation of the okara CNFs, as well as CA concentration, on the microstructure and physicochemical properties of the composite hydrogels. The water holding capacity, oil holding capacity, surface tension, gel strength, and viscoelasticity of the composite microgels increased with increasing CA concentration, and it was found that the highest values were obtained for TC-CA2 hydrogel: contact angle = 43.6° and surface tension = 45.12 mN/m, which was attributed to the formation of a more regular and dense three-dimensional gel network. All the CNF-CA microgels had highly anionic ζ-potential values (-38.8 to -50.1 mV), with the magnitude of the negative charge increasing with TEMPO oxidation and carrageenan concentration. These results suggest there would be strong electrostatic repulsion between the composite hydrogels. The composite microgels produced in our work may be useful functional materials for utilization within the food industry, thereby converting a waste product into a valuable commodity.

Cellulose from dinoflagellates as a versatile and environmentally friendly platform for the production of functionalised cellulose nanofibres.

Cellulose nanofibres (CNFs), also known as nano-fibrillated cellulose, have emerged as highly promising sustainable biomaterials owing to their numerous advantages, including high accessibility, long-term sustainability, low toxicity, and mechanical properties. Recently, marine organisms have been explored as novel and environmentally friendly sources of cellulose fibers (CFs) due to their easy cultivation, extraction and biocompatibility. Dinoflagellates, a group of marine phytoplankton, have gained particular attention due to their unique cellulosic morphology and lignin-free biomass. Previously, we showed that the unique amorphous nature of dinoflagellate-derived cellulose offers various benefits. This study further explores the potential of dinoflagellate-derived CFs as a sustainable and versatile CNF source. Extracted dinoflagellate cellulose is effectively converted into CNFs via one-step TEMPO oxidation without significant polymer degradation. In addition, the biological compatibility of the CNFs is improved by amine-grafting using putrescine and folic acid. The products are characterised by conductometric titration, zeta potential measurements, TGA, GPC, FTIR, SEM/TEM, XRD, and XPS. Finally, in a proof-of-principle study, the application of the functionalised CNFs in drug delivery is tested using methylene blue as a drug model. Our findings suggest that dinoflagellate-derived CNFs provide an eco-friendly platform that can be easily functionalised for various applications, including drug delivery.

Modulating the Release Kinetics of Natural Product Actinomycin from Bacterial Nanocellulose Films and Their Antimicrobial Activity.

The present study aimed to create a more sustainable and controlled delivery system based on natural biopolymer bacterial nanocellulose (BNC) and bacterial natural product actinomycin (Act), with the applicative potential in the biomedical field. In order to provide improved interaction between BNC and the active compound, and thus to modulate the release kinetics, the TEMPO oxidation of BNC support was carried out. A mix of actinomycins from bacterial fermentation (ActX) were used as natural antimicrobial agents with an established bioactivity profile and clinical use. BNC and TEMPO-oxidized BNC films with incorporated active compounds were obtained and analyzed by FTIR, SEM, XPS, and XRD. The ActX release profiles were determined in phosphate-buffer solution, PBS, at 37 °C over time. FTIR analysis confirmed the improved incorporation and efficiency of ActX adsorption on oxidized BNC due to the availability of more active sites provided by oxidation. SEM analysis indicated the incorporation of ActX into the less-dense morphology of the TEMPO-oxidized BNC in comparison to pure BNC. The release kinetics of ActX were significantly affected by the BNC structure, and the activated BNC sample indicated the sustained release of active compounds over time, corresponding to the Fickian diffusion mechanism. Antimicrobial tests using Staphylococcus aureus NCTC 6571 confirmed the potency of this BNC-based system for biomedical applications, taking advantage of the capacity of modified BNC to control and modulate the release of bioactive compounds.

Exploring Novel Applications for Hydrogels Derived from Modified Celluloses.

The valorization of lignocellulosic biomass by-products holds significant economic and ecological potential, considering their global overproduction. This paper introduces the fabrication of a novel wheat-straw-based hydrogel and a new microcellulose-based hydrogel through 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO) oxidation. In this study, Fourier transform infrared (FTIR) analysis was employed for the detection of carboxyl groups, neutralization titration was conducted using a conductivity meter, viscosity analysis was performed using a rheometer, and transmittance analysis was carried out using a spectrophotometer. Two novel hydrogels based on TEMPO oxidation have been developed. Among them, the bio-based hydrogel derived from oxidized wheat straw exhibited exceptional printability and injectability. We found that the oxidation degree of microcellulose reached 56-69%, and the oxidation degree of wheat straw reached 56-63%. The cross-linking of 4% oxidized wheat straw and calcium chloride was completed in 400 seconds, and the viscosity exceeded 100,000 Pa·s. In summary, we have successfully created low-cost hydrogels through the modification of wheat straw and microcellulose, transforming lignocellulosic biomass by-products into a sustainable source of polymers. This paper verifies the future applicability of biomass materials in 3D printing.

TEMPO-Oxidized Nanocellulose Films Modified by Tea Saponin Derived from Camellia oleifera: Physicochemical, Mechanical, and Antibacterial Properties.

Nanocellulose materials have been widely used in biomedicine, food packaging, aerospace, composite material, and other fields. In this work, cellulose obtained from Camellia shells through alkali boiling and subbleaching was micro-dissolved and regenerated using the DMAc (N,N-Dimethylacetamide)/LiCl system, and TOCNs (TEMPO-oxidized cellulose nanofibers) with different degrees of oxidation. The membrane was prepared by filtration of polytetrafluoroethylene (pore size 0.1 µm), and the oxidized nanocellulose film was obtained after drying, Then, the crystallinity, mechanical properties and oxygen barrier properties of the TOCN film were investigated. Furthermore, based on TS (tea saponin) from Camellia oleifera seed cake and TOCNs, TS-TOCN film was prepared by the heterogeneous reaction. The TS-TOCN film not only shows excellent oxygen barrier properties (the oxygen permeability is 2.88 cc·m-2·d-1) but also has good antibacterial effects on both Gram-negative and Gram-positive bacteria. The antibacterial property is comparable to ZnO-TOCN with the same antibacterial content prepared by the in-situ deposition method. Antioxidant activity tests in vitro showed that TS-TOCN had a significant scavenging effect on DPPH (2,2-Diphenyl-1-picrylhydrazyl) radicals. This design strategy makes it possible for inexpensive and abundant Camellia oleifera remainders to be widely used in the field of biobased materials.

A fast and sensitive colorimetric sensor for residual chlorine detection made with oxidized cellulose.

Residual chlorine from widespread disinfection processes forms byproducts in water that are harmful to humans and ecosystems. Portable sensors are essential tools for the on-site monitoring of residual chlorine in environmental samples. Here, an inexpensive colorimetric sensor was developed by grafting via amidation the chromogen orthotolidine (OTO) to the surface of a TEMPO-oxidized cellulose filter paper (O-TOFP). A thorough characterization of the sensor strip demonstrated that it was highly stable and that it could be stored for a long period before usage. O-TOFP had a fast response time of 30 s, was highly selective for residual chlorine ions (ClO-) with an accuracy of at least 95 %, and exhibited an excellent limit of detection of only 0.045 mg/L when combined with smartphone image acquisition. With its many positive features, the easy-to-use and robust O-TOFP sensor described here could become a useful tool for the determination of residual chlorine in different water samples.

Oxidation-induced starch molecular degradation: A comprehensive kinetic investigation using NaClO/NaBr/TEMPO system.

Starch degradation often coincides with its chemical modification, and understanding how chemical modification influences starch degradation is vital for determining the properties of the resultant modified products. This work investigates the effect of oxidation on starch molecular degradation, examining factors such as oxidation degree, reaction kinetics, and degradation patterns during 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated starch oxidation under varying conditions, including reaction time, pH, temperature, and concentrations of NaBr, TEMPO, and NaClO. Results emphasize that extended reaction durations primarily lead to ß-elimination, causing α-1,4 linkage cleavages. pH 8.5 favored non-selective oxidation, while pH 11 enhanced ß-elimination, both slowing the reaction rate and severely damaging starch chains (Mw of 8.8 × 105 g/mol and 7.2 × 105 g/mol, respectively). Elevated temperature from 0 to 30 °C significantly expedited both selective and non-selective oxidation, dramatically reducing molecular mass to 8.1 × 105 g/mol. Increasing concentrations of NaBr and TEMPO boost the reaction rate with minimal impact on molecular mass. Meanwhile, increasing NaClO concentration from 0.2 to 2.2 mmol/g-starch not only affects the reaction rate but also reinforces ß-elimination, enhancing molecular degradation. This study is insightful for starch modification to achieve desired oxidation levels and chain lengths by controlling reaction conditions, offering potential advancements in oxidized starch-based materials like nano micelles.

Nanolatex architectonics: Influence of cationic charge density and size on their adsorption onto surfaces with a 2D or 3D distribution of anionic groups.

HYPOTHESIS: It is theoretically predicted and hypothesized that the charge density and size of spherical nanoparticles are the key factors for their adsorption onto oppositely charged surfaces. It is also hypothesized that the morphology and charge of the surface are of great importance. In-plane 2D (silica) or a volumetric 3D (regenerated TEMPO-oxidized cellulose model surfaces) distribution of charged groups is expected to influence charge compensation and, thus, the adsorption behavior. EXPERIMENTS: In this work, self-stabilized nanolatexes with a range of cationic charge densities and sizes were synthesized through reversible addition - fragmentation chain-transfer (RAFT) polymerization coupled with polymerization-induced self-assembly (PISA). Their adsorption onto silica and anionic cellulose model surfaces was investigated using stagnation point adsorption reflectometry (SPAR) and quartz crystal microbalance with dissipation (QCM-D). FINDINGS: Experiments and theory agree and show that the size of the nanolatex and the difference in charge density compared to the substrate determine the charge compensation and, thus, the surface coverage. Highly charged or large nanolatexes overcompensate the surface charge of non-porous substrates leading to a significant repulsive zone where other particles cannot adsorb. For porous substrates like cellulose, the vertical distribution of charged groups in the 3D volume prevents overcompensation and thus increases the adsorption. This systematic study investigates the isolated effect of surface charge and size and paves the way for on-demand particles specifically designed for a surface with particular characteristics.

Multiscale Porous Carbon Materials by In Situ Growth of Metal-Organic Framework in the Micro-Channel of Delignified Wood for High-Performance Water Purification.

Porous carbon materials are suitable as highly efficient adsorbents for the treatment of organic pollutants in wastewater. In this study, we developed multiscale porous and heteroatom (O, N)-doped activated carbon aerogels (CAs) based on mesoporous zeolitic imidazolate framework-8 (ZIF-8) nanocrystals and wood using 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) oxidation, in situ synthesis, and carbonization/activation. The surface carboxyl groups in a TEMPO-oxidized wood (TW) can provide considerably large nucleation sites for ZIF-8. Consequently, ZIF-8, with excellent porosity, was successfully loaded into the TW via in situ growth to enhance the specific surface area and enable heteroatom doping. Thereafter, the ZIF-8-loaded TW was subjected to a direct carbonization/activation process, and the obtained activated CA, denoted as ZIF-8/TW-CA, exhibited a highly interconnected porous structure containing multiscale (micro, meso, and macro) pores. Additionally, the resultant ZIF-8/TW-CA exhibited a low density, high specific surface area, and excellent organic dye adsorption capacity of 56.0 mg cm-3, 785.8 m2 g-1, and 169.4 mg g-1, respectively. Given its sustainable, scalable, and low-cost wood platform, the proposed high-performance CA is expected to enable the substantial expansion of strategies for environmental protection, energy storage, and catalysis.

Tackling the challenge of drying and redispersion of cellulose nanofibrils via membrane-facilitated liquid phase exchange.

It is generally acknowledged that to advance the application of cellulose nanofibrils (CNFs) in product formulations, challenges associated with the drying and redispersion of this material must be addressed. Despite increased research efforts in this area, these interventions still involve the use of additives or conventional drying technologies, which both have the capacity to drive up the cost of the final CNF powders. Herein, we prepared dried and redispersible CNF powders with varying surface functionalities without the use of additives nor conventional drying technologies. Rapid drying in air was achieved after liquid phase exchange from water to isopropyl alcohol. The surface properties, morphology and thermal stabilities were the same for the never-dried and redispersed forms. The rheological properties of the CNFs were also unaffected after drying and redispersion of unmodified and organic acid modified materials. However, for 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO)-mediated oxidised CNFs with higher surface charge and longer fibrils, the storage modulus could not be recovered to the never-dried state because of the possible non-selective reduction in length upon redispersion. Nevertheless, this method provides an effective and low-cost process for the drying and redispersion of unmodified and surface modified CNFs.

Comparison of pre-treatments mediated by endoglucanase and TEMPO oxidation for eco-friendly low-cost energy production of cellulose nanofibrils.

Specific kinds of enzymes have been used as an eco-friendly pre-treatment for mechanical extraction of cellulose nanofibrils (CNFs) from vegetal pulps. Another well-established pre-treatment is the 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO)-mediated oxidation, which has gained considerable attention. Pre-treatments assist in fiber swelling, facilitating mechanical fibrillation, and reducing energy consumption; however, some of these methods are extremely expensive. This work aimed to evaluate the influence of enzymatic pre-treatment with endoglucanase on the energy consumption during mechanical fibrillation of cellulose pulps. Bleached pulps from Eucalyptus sp. and Pinus sp. were pre-treated with endoglucanase enzyme compared to TEMPO-meditated oxidation. Average diameters of CNFs pre-treated with enzymes were close to that found for TEMPO-oxidized nanofibrils (TOCNFs). Results showed that enzymatic pre-treatment did not significantly modify the pulp chemical and morphological characteristics with efficient stabilization of the CNFs suspension at higher supernatant turbidity. Energy consumption of pulps treated with endoglucanase enzymes was lower than that shown by pulps treated with TEMPO, reaching up to 58% of energy savings. The enzyme studied in the pulp treatment showed high efficiency in reducing energy consumption during mechanical fibrillation and production of films with high mechanical quality, being an eco-friendly option for pulp treatment.

Nanostructured Cellulose-Based Aerogels: Influence of Chemical/Mechanical Cascade Processes on Quality Index for Benchmarking Dye Pollutant Adsorbents in Wastewater Treatment.

(1) Background: Nanostructured cellulose has emerged as an efficient bio-adsorbent aerogel material, offering biocompatibility and renewable sourcing advantages. This study focuses on isolating (ligno)cellulose nanofibers ((L)CNFs) from barley straw and producing aerogels to develop sustainable and highly efficient decontamination systems. (2) Methods: (Ligno)cellulose pulp has been isolated from barley straw through a pulping process, and was subsequently deconstructed into nanofibers employing various pre-treatment methods (TEMPO-mediated oxidation process or PFI beater mechanical treatment) followed by the high-pressure homogenization (HPH) process. (3) Results: The aerogels made by (L)CNFs, with a higher crystallinity degree, larger aspect ratio, lower shrinkage rate, and higher Young's modulus than cellulose aerogels, successfully adsorb and remove organic dye pollutants from wastewater. (L)CNF-based aerogels, with a quality index (determined using four characterization parameters) above 70%, exhibited outstanding contaminant removal capacity over 80%. The high specific surface area of nanocellulose isolated using the TEMPO oxidation process significantly enhanced the affinity and interactions between hydroxyl and carboxyl groups of nanofibers and cationic groups of contaminants. The efficacy in adsorbing cationic dyes in wastewater onto the aerogels was verified by the Langmuir adsorption isotherm model. (4) Conclusions: This study offers insights into designing and applying advanced (L)CNF-based aerogels as efficient wastewater decontamination and environmental remediation platforms.

Partial acid-hydrolysis of TEMPO-oxidized arabinoxylans generates arabinoxylan-structure resembling oligosaccharides.

Arabinoxylans (AXs) display biological activities that depend on their chemical structures. To structurally characterize and distinguish AXs using a non-enzymatic approach, various TEMPO-oxidized AXs were partially acid-hydrolysed to obtain diagnostic oligosaccharides (OS). Arabinurono-xylo-oligomer alditols (AUXOS-A) with degree of polymerization 2-5, comprising one and two arabinuronic acid (AraA) substituents were identified in the UHPLC-PGC-MS profiles of three TEMPO-oxidized AXs, namely wheat (ox-WAX), partially-debranched WAX (ox-pD-WAX), and rye (ox-RAX). Characterization of these AUXOS-A highlighted that single-substitution of the Xyl unit preferably occurs at position O-3 for these samples, and that ox-WAX has both more single substituted and more double-substituted xylose residues in its backbone than the other AXs. Characteristic UHPLC-PGC-MS OS profiles, differing in OS abundance and composition, were obtained for each AX. Thus, partial acid-hydrolysis of TEMPO-oxidized AXs with analysis of the released OS by UHPLC-PGC-MS is a promising novel non-enzymatic approach to distinguish AXs and obtain insights into their structures.