Browse
Submit Data
Databases
API
Help

Dataset Information

10 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

A molecular scale analysis of TEMPO-oxidation of native cellulose molecules

ABSTRACT: The native cellulose, through TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical)-mediated oxidation, can be converted into individual fibers. It has been observed that oxidized fibers disperse completely and individually in water. It is believed that electrostatic repulsive forces might be responsible for such observations. In order to study the TEMPO-oxidation of cellulose molecules, we used Density Functional Theory (DFT) calculations and Flory-Huggins theory combined with molecular dynamics (MD). The surface electrostatic potential in native cellulose and TEMPO-oxidized cellulose were calculated using DFT calculations. We found that TEMPO-oxidized cellulose accommodates a threefold screw conformation where the negatively charged (–COO–) functional groups are pointed away from the surface in all spatial directions. This spatial orientation causes that TEMPO-oxidized cellulose molecules repulse each other due to strong negatively charged surface. At the same time, the spatial orientation increases the hydrophilicity in TEMPO-oxidized cellulose molecules. These observations explain the improved dispersion in water and separability of TEMPO-oxidized cellulose molecules. We obtained large and positive Flory–Huggins interaction parameters for TEMPO-oxidized cellulose molecules indicating their higher dispersion once in water. Cellulose; TEMPO oxidation; Density functional theory; Molecular dynamics; Surface modification

SUBMITTER: Asgarpour Khansary M

PROVIDER: S-EPMC7779718 | biostudies-literature | 2020 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Lignin-Containing Cellulose Nanofibrils from TEMPO-Mediated Oxidation of Date Palm Waste: Preparation, Characterization, and Reinforcing Potential.

Project description:Lignin-containing cellulose nanofibrils (LCNFs) have emerged as a new class of nanocelluloses where the presence of residual lignin is expected to impart additional attributes such as hydrophobicity or UV-absorption. In the present work, LCNFs with a lignin content between 7 and 15 wt% were prepared via a TEMPO-mediated oxidation as chemical pretreatment followed by high-pressure homogenization. The impact of the carboxyl content (CC) on the properties of the resulting LCNF gel, in terms of lignin content, colloidal properties, morphology, crystallinity, and thermal stability, were investigated. It was found that lignin content was significantly decreased at increasing CC. In addition, CC had a positive effect on colloidal stability and water contact angle, as well as resulting in smaller fibrils. This lower size, together with the lower lignin content, resulted in a slightly lower thermal stability. The reinforcing potential of the LCNFs when incorporated into a ductile polymer matrix was also explored by preparing nanocomposite films with different LCNF contents that were mechanically tested under linear and non-linear regimes by dynamic mechanical analysis (DMA) and tensile tests. For comparison purposes, the reinforcing effect of the LCNFs with lignin-free CNFs was also reported based on literature data. It was found that lignin hinders the network-forming capacity of LCNFs, as literature data shows a higher reinforcing potential of lignin-free CNFs. Nonetheless, the tensile strength of the acrylic matrix was enhanced by 10-fold at 10 wt% of LCNF content.

| S-EPMC9824203 | biostudies-literature

One-Pot Method of Synthesizing TEMPO-Oxidized Bacterial Cellulose Nanofibers Using Immobilized TEMPO for Skincare Applications.

Project description:In the skincare field, water-dispersed bacterial cellulose nanofibers synthesized via an oxidation reaction using 2,2,6,6-tetramethyl-1-piperidine-N-oxy radical (TEMPO) as a catalyst are promising bio-based polymers for engineered green materials because of their unique properties when applied to the surface of the skin, such as a high tensile strength, high water-holding capacity, and ability to block harmful substances. However, the conventional method of synthesizing TEMPO-oxidized bacterial cellulose nanofibers (TOCNs) is difficult to scale due to limitations in the centrifuge equipment when treating large amounts of reactant. To address this, we propose a one-pot TOCN synthesis method involving TEMPO immobilized on silica beads that employs simple filtration instead of centrifugation after the oxidation reaction. A comparison of the structural and physical properties of the TOCNs obtained via the proposed and conventional methods found similar properties in each. Therefore, it is anticipated that due to its simplicity, efficiency, and ease of use, the proposed one-pot synthesis method will be employed in production scenarios to prepare production quantities of bio-based polymer nanofibers in various potential industrial applications in the fields of skincare and biomedical research.

| S-EPMC6631351 | biostudies-literature

Copper/TEMPO Redox Redux: Analysis of PCET Oxidation of TEMPOH by Copper(II) and the Reaction of TEMPO with Copper(I).

Project description:Copper salts and organic aminoxyls, such as TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl), are versatile catalysts for aerobic alcohol oxidation. Previous reports in the literature contain conflicting proposals concerning the redox interactions that take place between copper(I) and copper(II) salts with the aminoxyl and hydroxylamine species, TEMPO and TEMPOH, respectively. Here, we reinvestigate these reactions in an effort to resolve the conflicting claims in the literature. Under anaerobic conditions, CuIIX2 salts [X = acetate (OAc), trifluoroacetate (TFA), and triflate (OTf)] are shown to promote the rapid proton-coupled oxidation of TEMPOH to TEMPO: CuIIX2 + TEMPOH → CuIX + TEMPO + HX. In the reaction with acetate, however, slow reoxidation of CuIOAc occurs. This process requires both TEMPO and HOAc and coincides with the reduction of TEMPO to 2,2,6,6-tetramethylpiperidine. Analogous reactivity is not observed with trifluoroacetate and triflate species. Overall, the facility of the proton-coupled oxidation of TEMPOH by CuII salts suggests that this process could contribute to catalyst regeneration under aerobic oxidation conditions.

| S-EPMC7641458 | biostudies-literature

DFT Optimization of Isolated Molecular Chain Sheet Models Constituting Native Cellulose Crystal Structures.

Project description:Because of high crystallinity and natural abundance, the crystal structures of the native cellulose allomorphs have been theoretically investigated to elucidate the cellulose chain packing schemes. Here, we report systematic structure optimization of cellulose chain sheet models isolated from the cellulose Iα and Iβ crystals by density functional theory (DFT). For each allomorph, the three-dimensional chain packing structure was partitioned along each of the three main crystal planes to construct either a flat chain sheet model or two stacked chain sheet models, each consisting of four cello-octamers. Various combinations of the basis set and DFT functional were investigated. The flat chain sheet models constituting the cellulose Iα (110) and Iβ (100) planes, where the cellulose chains are mainly linked by intermolecular hydrogen bonds, exhibit a right-handed twist. More uniform and symmetrical sheet twists are observed when the flat chain sheet models are optimized using a basis set with diffuse functions (6-31+G(d,p)). The intermolecular interactions are more stable when the chain sheet models are optimized with the two hybrid functionals CAM-B3LYP and M06-2X. Optimization of the two stacked chain sheet models, where van der Waals interactions predominated between adjacent chains, gave differing results; those retaining the initial structures and those losing the sheet appearance, corresponding to the cellulose Iα/Iβ (010)/(11̅0) and (100)/(110) chain sheet models, respectively. The cellulose Iβ (11̅0) chain sheet model is more stable using the M06-2X functional than using the CAM-B3LYP functional.

| S-EPMC6644672 | biostudies-literature

Molecular-scale visualization of sarcomere contraction within native cardiomyocytes.

Project description:Sarcomeres, the basic contractile units of striated muscle, produce the forces driving muscular contraction through cross-bridge interactions between actin-containing thin filaments and myosin II-based thick filaments. Until now, direct visualization of the molecular architecture underlying sarcomere contractility has remained elusive. Here, we use in situ cryo-electron tomography to unveil sarcomere contraction in frozen-hydrated neonatal rat cardiomyocytes. We show that the hexagonal lattice of the thick filaments is already established at the neonatal stage, with an excess of thin filaments outside the trigonal positions. Structural assessment of actin polarity by subtomogram averaging reveals that thin filaments in the fully activated state form overlapping arrays of opposite polarity in the center of the sarcomere. Our approach provides direct evidence for thin filament sliding during muscle contraction and may serve as a basis for structural understanding of thin filament activation and actomyosin interactions inside unperturbed cellular environments.

| S-EPMC8253822 | biostudies-literature

Mechanism of copper(I)/TEMPO-catalyzed aerobic alcohol oxidation.

Project description:Homogeneous Cu/TEMPO catalyst systems (TEMPO = 2,2,6,6-tetramethylpiperidine-N-oxyl) have emerged as some of the most versatile and practical catalysts for aerobic alcohol oxidation. Recently, we disclosed a (bpy)Cu(I)/TEMPO/NMI catalyst system (NMI = N-methylimidazole) that exhibits fast rates and high selectivities, even with unactivated aliphatic alcohols. Here, we present a mechanistic investigation of this catalyst system, in which we compare the reactivity of benzylic and aliphatic alcohols. This work includes analysis of catalytic rates by gas-uptake and in situ IR kinetic methods and characterization of the catalyst speciation during the reaction by EPR and UV-visible spectroscopic methods. The data support a two-stage catalytic mechanism consisting of (1) "catalyst oxidation" in which Cu(I) and TEMPO-H are oxidized by O(2) via a binuclear Cu(2)O(2) intermediate and (2) "substrate oxidation" mediated by Cu(II) and the nitroxyl radical of TEMPO via a Cu(II)-alkoxide intermediate. Catalytic rate laws, kinetic isotope effects, and spectroscopic data show that reactions of benzylic and aliphatic alcohols have different turnover-limiting steps. Catalyst oxidation by O(2) is turnover limiting with benzylic alcohols, while numerous steps contribute to the turnover rate in the oxidation of aliphatic alcohols.

| S-EPMC3834274 | biostudies-literature

Noncovalent Immobilization of Molecular Electrocatalysts for Chemical Synthesis: Efficient Electrochemical Alcohol Oxidation with a Pyrene-TEMPO Conjugate.

Project description:Electrocatalytic methods for organic synthesis could offer sustainable alternatives to traditional redox reactions, but strategies are needed to enhance the performance of molecular catalysts designed for this purpose. The synthesis of a pyrene-tethered TEMPO derivative (TEMPO=2,2,6,6-tetramethylpiperidinyl-N-oxyl) is described, which undergoes facile in?situ noncovalent immobilization onto a carbon cloth electrode. Cyclic voltammetry and controlled potential electrolysis studies demonstrate that the immobilized catalyst exhibits much higher activity relative to 4-acetamido-TEMPO, an electronically similar homogeneous catalyst. In preparative electrolysis experiments with a series of alcohol substrates and the immobilized catalyst, turnover numbers and frequencies approach 2?000 and 4?000?h-1 , respectively. The synthetic utility of the method is further demonstrated in the oxidation of a sterically hindered hydroxymethylpyrimidine precursor to the blockbuster drug, rosuvastatin.

| S-EPMC5831151 | biostudies-literature

Interfacial Hydrolysis of Acetals on Protonated TEMPO-oxidized Cellulose Nanofibers.

Project description:2,2,6,6-Tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanofibers (TOCNs), which have a high-density of exposed carboxylic acid groups on their crystalline surfaces, effectively act as acid catalysts in acetal hydrolysis. Carboxy-free cellulose nanofibers, polymeric carboxylic acids, and homogeneous acetic acid do not show significant catalytic activity under the same reaction conditions. Mercerized TOCNs differing from the original TOCNs in a crystalline structure were also ineffective, which suggests that the unique nanoarchitectural features of TOCNs, such as regularly aligned carboxylic acid groups, large specific surface areas, and structural rigidity, must be major factors in the acceleration of acetal hydrolysis. Kinetic analysis suggested that substrates and/or acid catalyst species were concentrated on the TOCN crystalline surfaces, which significantly enhanced the catalytic activity.

| S-EPMC5864833 | biostudies-other

TEMPO-Cellulose Nanocrystal-Capped Gold Nanoparticles for Colorimetric Detection of Pathogenic DNA.

Project description:Nanocellulose-assisted gold nanoparticles are considered promising materials for developing eco-friendly diagnostic tools for biosensing applications. In this study, we synthesized 2,2,6,6-tetramethylpiperidin-1-piperidinyloxy (TEMPO)-oxidized cellulose nanocrystal (TEMPO-CNC)-capped gold nanoparticles (AuNPs) for the colorimetric detection of unamplified pathogenic DNA oligomers of methicillin-resistant Staphylococcus aureus. The fabricated TEMPO-CNC-AuNPs (TC-AuNPs) were characterized using UV-visible spectroscopy, transmission electron microscopy, atomic force microscopy, and dynamic light scattering. The average diameter of the synthesized AuNPs was approximately 30 nm. The aqueous solution of TC-AuNPs was stable and exhibited an absorption peak at 520 nm. The chemical interaction between TC-AuNPs and the surface charge of the target and non-target DNA determined the colorimetric differences under ionic conditions. A dramatic color change (red → blue) was observed in the TC-AuNP solution with the target DNA under ionic conditions due to the aggregation of AuNPs. However, no observable color change occurred in the TC-AuNP solution with the non-target DNA under similar conditions owing to the better shielding effects of the charged moieties. The colorimetric detection limit of the TC-AuNPs was demonstrated to be as low as 20 fM pathogenic DNA. Therefore, the use of TEMPO-oxidized CNC-capped AuNPs is efficient and straightforward as a biosensor for the colorimetric detection of pathogenic DNA.

| S-EPMC8154114 | biostudies-literature

Chemoselektive γ‐Oxidation von β,γ‐ungesattigten Amiden mit TEMPO

Project description: Not available

| S-EPMC10946935 | biostudies-literature