Films based on TEMPO-oxidized chitosan nanoparticles: Obtaining and potential application as wound dressings.

A series of novel films based on TEMPO-oxidized chitosan nanoparticles were prepared by casting method. Fourier transform infrared spectroscopy (FTIR) was employed to ascertain the chemical structure of TEMPO-oxidized chitosan. The surface morphology of the TEMPO-oxidized chitosan nanoparticles was analyzed by atomic force microscopy (AFM). The physicochemical (area density, thickness, iodine sorption, roughness), functional (moisture sorption, liquid absorption capacity, weight loss upon contact with the liquid, and water vapor transmission rate), antibacterial, and antioxidant properties of films based on TEMPO-oxidized chitosan nanoparticles were also investigated. The physicochemical properties of the films varied widely: area density ranged from 77.83 ± 0.06 to184.46 ± 0.05 mg/cm2, thickness varied between 80.5 ± 1.6 and 200.5 ± 1.6 µm, iodine sorption spanned from 333.7 ± 2.1 to166.4 ± 2.2 mg I2/g, and roughness ranged from 4.1 ± 0.2 to 5.6 ± 0.3 nm. Similarly, the functional properties also varied significantly: moisture sorption ranged from 4.76 ± 0.03 to 9.62 ± 0.11 %, liquid absorption capacity was between 129.04 ± 0.24 and 159.33 ± 0.73 % after 24 h, weight loss upon contact with the liquid varied between 31.06 ± 0.35 and 45.88 ± 0.58 % after 24 h and water vapor transmission rate ranged from 1220.10 ± 2.91to1407.77 ± 5.22 g/m2 day. Despite the wide variations in physicochemical and functional properties, all films showed maximum bacterial reduction of Staphylococcus aureus and Escherichia coli, although they exhibited low antioxidant activity. The results suggest that the films could be effectively utilized as antibacterial wound dressings.

A novel strategy and characteristics of PVA/citric acid cross-linked hydrophilic elastic sponge of cellulose based on medicinal herb residue.

A new ultra-hydrophilic elastic sponge composite has been proposed. Medicinal herbs, commonly used in herbal medicine and subsequently discarded, are rich in natural polymer substances, making them promising candidates for various material industries. TEMPO-oxidized cellulose was extracted from medicinal herb residue, and the physicochemical properties of an ultra-hydrophilic elastic sponge, prepared through a PVA and CA impregnate cross-linking process, were investigated. The fabricated composite sponge exhibited an increase in compressive stress-strain proportional to the PVA cross-linking concentration, and its water retention capability was assessed through retention tests. Swelling tests for various solvents were conducted to evaluate the potential use of the sponge in diverse industries, revealing the highest swelling ratio in water. Pressure distribution measurements using prescale film indicated that the sponge's shock absorption capacity was enhanced by PVA cross-linking, leading to improved pressure dispersion.

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.

Eco-friendly cellulose-based antioxidation film by partial esterification.

Cellulose nanocrystals (CNCs) have received increasing attention because of their superior dispersion and thermal stability. In this study, TEMPO-oxidized cellulose nanocrystal (TOCNC) multifunctional antioxidationantioxidation films (TOCNC-GA film) were prepared by the esterification of TOCNC and gallic acid (GA). TOCNC-GAX films, where X represents the ratio of the amount of GA to the amount of TOCNC, were characterized using scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The films with the GA:TOCNC ratio of 1:1 achieved higher interfacial compatibility than the other films. The mechanical properties and water resistance of the TOCNC-GA films were superior than those of pure TOCNC films. Moreover, the original TOCNC structure changed owing to the presence of GA, which endowed a certain thermoplasticity owing to the formation of ester groups. The antioxidation properties of the TOCNC-GA1 films reached 43.8 % and 71.85 % after 6 and 24 h, respectively, as evaluated by the 2,2-biphenyl-1-picrylhydrazyl method and the free radical scavenging activities of the TOCNC-GA1 films. The innovative development of the functional antioxidation film presented in this paper has great potential for use in antioxidation packaging materials and food preservation.

Nanocellulose extraction from acai bagasse through mixed acid hydrolysis and oxidative techniques.

Exploring new biomass sources for nanocellulose (NC) extraction is crucial in elevating the economic value of readily available renewable resources. This study compares NC extracted from acai (Euterpe oleracea) bagasse using different methods: mixed acid hydrolysis, 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO) mediation, and ammonium persulfate (APS) oxidations. A comprehensive analysis investigates the impact of each treatment on the physical-chemical properties of the nanoparticles, including chemical structure, crystallinity, morphology, and thermal and suspension stability. NCs obtained through mixed acid hydrolysis exhibit the highest crystallinity (62 %) and low sulfate groups on their surfaces. Consequently, they demonstrate excellent thermal stability but poor colloidal stability in water. Oxidized NCs undergo chemical modification, converting alcoholic groups into carboxyl, resulting in NCs with zeta potentials ranging between -25.30 ± 0.81 and - 27.49 ± 1.07 mV. APS oxidation produces nanoparticles with superior thermal stability compared to TEMPO oxidation. Atomic Force Microscopy (AFM) images reveal that all nanocelluloses share characteristics of nanofibers (CNFs). This comprehensive characterization highlights the potential of acai bagasse for yielding high-added-value bioproducts suitable for versatile applications.

Modification and characterization of a novel and fluorine-free cellulose nanofiber with hydrophobic and oleophobic properties.

In this study, a brand-new, easy, and environmentally friendly approach for chemically functionalizing 2,2,6,6-tetramethylpiperidinyloxyl radical (TEMPO)-oxidized cellulose nanofiber (TOCNF) to produce modified cellulose nanofiber (octadecylamine-citric acid-CNF) was proposed. Effects of octadecylamine (ODA)/TOCNF mass ratio on the chemical structure, morphology, surface hydrophobicity and oleophobicity were studied. According to Fourier transform infrared spectroscopy (FTIR) analysis, ODA was successfully grafted onto the TOCNF by simple citric acid (CA) esterification and amidation reactions. Scanning electron microscopy (SEM) showed that a new rough structure was formed on the ODA-CA-CNF surface. The water contact angle (WCA) and the castor oil contact angle (OCA) of the ODA-CA-CNF reached 139.6° and 130.6°, respectively. The high-grafting-amount ODA-CA-CNF was sprayed onto paper, and the OCA reached 118.4°, which indicated good oil-resistance performance. The low-grafting-amount ODA-CNF was applied in a pH-responsive indicator film, exhibiting a colour change in response to the pH level, which can be applied in smart food packaging. The ODA-CA-CNF with excellent water/oil-resistance properties and fluorine-free properties can replace petrochemical materials and can be used in the fields of fluorine-free oil-proof paper.

Structure Formation by 3D-Printing of Cellulose from Cellulose-NMMO-Water Solutions: Analysis of Extrusion, Regeneration, and Drying Stages.

Processing cellulose from 4-methyl morpholine n-oxide (NMMO)-water solutions is a completely circular route that produces biodegradable cellulose fibers or films while recovering reusable NMMO [Guo, Y.; Cai, J.; Sun, T.; Xing, L.; Cheng, C.; Chi, K.; Xu, J.; Li, T. The purification process and side reactions in the N-methylmorpholine-N-oxide (NMMO) recovery system. Cellulose 2021, 28(12), 7609-7617]. Despite proven success in two-dimensional applications, challenges in transitioning to three-dimensional objects arise from the critical changes that cellulose undergoes during deposition, regeneration, and postregeneration stages. While emphasizing the critical diffusion-driven precipitation during regeneration, this investigation explores the influence of extrusion temperature, printing alignment, regeneration, and drying processes on interfilament fusion, bonding, shape integrity, and mechanical properties. Three distinct drying processes: ambient, vacuum, and freeze-drying were investigated. Tensile and flexural bending tests provided insight into the delamination of dried specimens. Ambient and vacuum drying enhanced the properties of specimens, while freeze-drying resulted in a more stable shape. The findings contribute to advancing the understanding of 3D-printing cellulose from NMMO solutions, addressing crucial aspects of the extrusion, regeneration, and drying stages for enhanced applications in sustainable manufacturing.

Investigating the impact of cellulose microgel nanofabrication on the rheological properties of this binary rheology modifier.

The multifunctionality of advanced laundry detergents primarily relies on the inclusion of functional solid particles, such as pearlescent powder, enzymes, and perfume microcapsules. However, the high-content surfactants in these detergents can render most existing suspending rheology modifiers ineffective, making it challenging to achieve uniform suspension of these functional particles. This compromises the overall functionality of laundry products. To address this, we have developed a binary rheology modifier comprising cellulose microgel and HPMC (hydroxypropyl methylcellulose), acting as the "island" and "chain," respectively. Together, they form an interconnected dynamic network that effectively "encapsulates" the functional particles. Furthermore, the cellulose microgel/HPMC rheology modifier demonstrates versatility, proving effective with various surfactants. Despite its potential, the suspension mechanism of cellulose microgel/HPMC remains elusive. Therefore, we conducted a comprehensive investigation, fabricating cellulose microgels with varying nanofabrication degrees and surface charges through TEMPO oxidation. Our findings highlight the critical role of the surficial structure of T-Microgel, specifically its nanofabrication degree, in influencing the dynamic network's fabrication, thereby impacting yield and thixotropic properties. The surface charge of T-microgel does not significantly influence the process. This research not only elucidates the intricate dynamics of cellulose microgel/HPMC interaction but also provides fundamental insights essential for the development of innovative rheology modifiers tailored for high-content surfactant applications.

Dextran Macroinitiator for Synthesis of Polysaccharide-b-Polypeptide Block Copolymers via NCA Ring-Opening Polymerization.

Synthesis of polysaccharide-b-polypeptide block copolymers represents an attractive goal because of their promising potential in delivery applications. Inspired by recent breakthroughs in N-carboxyanhydride (NCA) ring-opening polymerization (ROP), we present an efficient approach for preparation of a dextran-based macroinitiator and the subsequent synthesis of dextran-b-polypeptides via NCA ROP. This is an original approach to creating and employing a native polysaccharide macroinitiator for block copolymer synthesis. In this strategy, regioselective (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) oxidation of the sole primary alcohol located at the C-6 position of the monosaccharide at the nonreducing end of linear dextran results in a carboxylic acid. This motif is then transformed into a tetraalkylammonium carboxylate, thereby generating the dextran macroinitiator. This macroinitiator initiates a wide range of NCA monomers and produces dextran-b-polypeptides with a degree of polymerization (DP) of the polypeptide up to 70 in a controlled manner (D < 1.3). This strategy offers several distinct advantages, including preservation of the original dextran backbone structure, relatively rapid polymerization, and moisture tolerance. The dextran-b-polypeptides exhibit interesting self-assembly behavior. Their nanostructures have been investigated by dynamic light scattering (DLS) and transmission electron microscopy (TEM), and adjustment of the structure of block copolymers allows self-assembly of spherical micelles and worm-like micelles with varied diameters and aspect ratios, revealing a range of diameters from 60 to 160 nm. Moreover, these nanostructures exhibit diverse morphologies, including spherical micelles and worm-like micelles, enabling delivery applications.

Controllable radical polymerization of TEMPO redox for stable and sensitive enzyme electrode interface.

Assembling functional molecules on the surface of an enzyme electrode is the most basic technique for constructing a biosensor. However, precise control of electron transfer interface or electron mediator on the electrode surface remains a challenge, which is a key step that affects the stability and sensitivity of enzyme-based biosensors. In this study, we propose the use of controllable free radical polymerization to grow stable 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) polymer as electron mediator on enzyme surface for the first time. Through scanning electron microscopy (SEM), Raman spectroscopy, electrode surface coverage measurement, static contact angle (SCA), and a series of electrochemical methods, it has been demonstrated that the TEMPO-based enzyme electrode exhibits a uniform hydrophilic morphology and stable electrochemical performance. Furthermore, the results show that the sensor demonstrates high sensitivity for detecting glucose biomolecules in artificial sweat and serum. Attributing to the quantitative and controllable radical polymerization of TEMPO redox assembled enzyme electrode surface, the as-proposed biosensor providing a use, storage, and inter-batch sensing stability, providing a vital platform for wearable/implantable biochemical sensors.

A chemo-enzymatic pathway to expand cellooligosaccharide chemical space through amine bond introduction.

Enzymatic functionalization of oligosaccharides is a useful and environmentally friendly way to expand their structural chemical space and access to a wider range of applications in the health, food, feed, cosmetics and other sectors. In this work, we first tested the laccase/TEMPO system to generate oxidized forms of cellobiose and methyl ß-D-cellobiose, and obtained high yields of novel anionic disaccharides (>60 %) at pH 6.0. Laccase/TEMPO system was then applied to a mix of cellooligosaccharides and to pure D-cellopentaose. The occurrence of carbonyl and carboxyl groups in the oxidation products was shown by LC-HRMS, MALDI-TOF and reductive amination of the carbonyl groups was attempted with p-toluidine a low molar mass amine to form the Schiff base, then reduced by 2-picoline borane to generate a more stable amine bond. The new grafted products were characterized by LC-HRMS, LC-UV-MS/MS and covalent grafting was evidenced. Next, the same procedure was adopted to successfully graft a dye, the rhodamine 123, larger in size than toluidine. This two-step chemo-enzymatic approach, never reported before, for functionalization of oligosaccharides, offers attractive opportunities to anionic cellooligosaccharides and derived glucoconjugates of interest for biomedical or neutraceutical applications. It also paves the way for more environmentally-friendly cellulose fabric staining procedures.

Stabilization mechanisms and digestion properties of Pickering emulsions prepared with tempo-oxidized hyaluronic acid/chitosan nanoparticles: From the perspective of oxidation degree.

In this study, the stabilization mechanism and digestion behavior of Pickering emulsion prepared by a combination of chitosan (CS) and TEMPO-oxidized hyaluronic acid (HA) were investigated. Conductometric titration was used to determine the degree of oxidation and carboxylate content of TEMPO-oxidized HA. The results showed that the degree of oxidation increased proportionally with increasing oxidation time, and the electrostatic and hydrogen bonding interactions with CS were significantly enhanced. The results of FTIR and TEM showed the formation of CS/oxidized HA nanoparticles (CS/oxidized-HANPs). In addition, the contact angle of CS/oxidized-HANPs is closed to 77°, thereby providing higher desorption energy at the interface. Rheological results showed that the Pickering emulsion exhibited a gel-like network structure and higher viscosity. In vitro digestion results suggested that the quercetin (Que) bioaccessibility of the CS/oxidation HANps-stabilized Pickering emulsion with an oxidation time of 20 min was better than that of the conventional emulsion prepared with CS alone. The research is expected to develop novel polysaccharide-based Pickering emulsion delivery systems for functional compounds.

Harmonizing Energies: The Interplay Between a Nonplanar SalEn-Type Molecule and a TEMPO Moiety in a New Hybrid Energy-Storing Redox-Conducting Polymer.

Redox-conducting polymers based on SalEn-type complexes have attracted considerable attention due to their potential applications in electrochemical devices. However, their charge transfer mechanisms, physical and electrochemical properties remain unclear, hindering their rational design and optimization. This study aims to establish the influence of monomer geometry on the polymer's properties by investigating the properties of novel nonplanar SalEn-type complexes, poly[N,N'-bis(salicylidene)propylene-2-(hydroxy)diaminonickel(II)], and its analog with 2,2,6,6-tetramethylpiperidinyl-N-oxyl (TEMPO)-substituted bridge (MTS). To elucidate the charge transfer mechanism, operando UV-Vis spectroelectrochemical analysis, electrochemical impedance spectroscopy, and electron paramagnetic resonance are employed. Introducing TEMPO into the bridge moiety enhanced the specific capacity of the poly(MTS) material to 95 mA h g-1, attributed to TEMPO's and conductive backbone's charge storage capabilities. Replacement of the ethylenediimino-bridge with a 1,3-propylenediimino- bridge induced significant changes in the complex geometry and material's morphology, electrochemical, and spectral properties. At nearly the same potential, polaron and bipolaron particles emerged, suggesting intriguing features at the overlap point of the electroactivity potentials ranges of polaron-bipolaron and TEMPO, such as a disruption in the connection between TEMPO and the conjugation chain or intramolecular charge transfer. These results offer valuable insights for optimizing strategies to create organic materials with tailored properties for use in catalysis and battery applications.

Scandium Ion-Promoted Electron-Transfer Disproportionation of 2-Phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl 3-Oxide (PTIO•) in Acetonitrile and Its Regeneration Induced by Water.

2-Phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl 3-oxide (PTIO•), a persistent nitronyl nitroxide radical, has been used for the detection and trapping of nitric oxide, as a redox mediator for batteries, for the activity estimation of antioxidants, and so on. However, there is no report on the reactivity of PTIO• in the presence of redox-inactive metal ions. In this study, it is demonstrated that the addition of scandium triflate, Sc(OTf)3 (OTf = OSO2CF3), to an acetonitrile (MeCN) solution of PTIO• resulted in an electron-transfer disproportionation to generate the corresponding cation (PTIO+) and anion (PTIO-), the latter of which is suggested to be stabilized by Sc3+ to form [(PTIO)Sc]2+. The decay of the absorption band at 361 nm due to PTIO•, monitored using a stopped-flow technique, obeyed second-order kinetics. The second-order rate constant for the disproportionation, thus determined, increased with increasing the Sc(OTf)3 concentration to reach a constant value. A drastic change in the cyclic voltammogram recorded for PTIO• in deaerated MeCN containing 0.10 M Bu4NClO4 was also observed upon addition of Sc(OTf)3, suggesting that the large positive shift of the one-electron reduction potential of PTIO• (equivalent to the one-electron oxidation potential of PTIO-) in the presence of Sc(OTf)3 may result in the disproportionation. When H2O was added to the PTIO•-Sc(OTf)3 system in deaerated MeCN, PTIO• was completely regenerated. It is suggested that the complex formation of Sc3+ with H2O may weaken the interaction between PTIO- and Sc3+, leading to electron-transfer comproportionation to regenerate PTIO•. The reversible disproportionation of PTIO• was also confirmed by electron paramagnetic resonance (EPR) spectroscopy.

Design, synthesis, and biological evaluation of dinaciclib and CAN508 hybrids as CDK inhibitors.

The scaffolds of two known CDK inhibitors (CAN508 and dinaciclib) were the starting point for synthesizing two series of pyarazolo[1,5-a]pyrimidines to obtain potent inhibitors with proper selectivity. The study presented four promising compounds; 10d, 10e, 16a, and 16c based on cytotoxic studies. Compound 16a revealed superior activity in the preliminary anticancer screening with GI % = 79.02-99.13 against 15 cancer cell lines at 10 µM from NCI full panel 60 cancer cell lines and was then selected for further investigation. Furthermore, the four compounds revealed good safety profile toward the normal cell lines WI-38. These four compounds were subjected to CDK inhibitory activity against four different isoforms. All of them showed potent inhibition against CDK5/P25 and CDK9/CYCLINT. Compound 10d revealed the best activity against CDK5/P25 (IC50 = 0.063 µM) with proper selectivity index against CDK1 and CDK2. Compound 16c exhibited the highest inhibitory activity against CDK9/CYCLINT (IC50 = 0.074 µM) with good selectivity index against other isoforms. Finally, docking simulations were performed for compounds 10e and 16c accompanied by molecular dynamic simulations to understand their behavior in the active site of the two CDKs with respect to both CAN508 and dinaciclib.

Algal growth inhibition test with TEMPO-oxidized cellulose nanofibers.

Ecotoxicity data on cellulose nanofibers (CNFs) are limited despite their wide potential applications prospects, such as structural and packaging materials, filters, coatings, foods, and cosmetics. In this study, toxicity tests of 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized CNFs (TEMPO-CNFs), which are one of the major CNF products commercially available in Japan, on the green alga Raphidocelis subcapitata were conducted. As nanomaterials are considered difficult-to-test substances, the Organisation for Economic Co-operation and Development has released a guidance document that provides considerations regarding ecotoxicity tests of nanomaterials. In the algal growth inhibition tests of TEMPO-CNFs, there were specific issues to be examined, including the effects of medium components on the characteristics of TEMPO-CNFs, CNF interference with algal density measurements, algal interference with CNF measurements, and the effects of ion concentration changes in the test medium by the addition of CNFs on algal growth. To examine these issues, we conducted preliminary studies and established a suitable test method for algal growth inhibition tests of TEMPO-CNFs. We confirmed that the components in the medium for algal growth inhibition tests had negligible effects on the characteristics (zeta-potential, viscosity, and morphology) and concentration stability of TEMPO-CNFs and that in vitro and in vivo fluorescence measurements were applicable for estimating the algal densities, without interference by TEMPO-CNFs. In contrast, we observed that the grown algae interfered with the CNF concentration measurements. Therefore, we established a method to correct the measured CNF concentrations by estimating the algal contribution. Furthermore, we found that the nutrient salt concentrations in the medium changed due to interactions with CNFs; however, this change did not affect algal growth. Based on the results of the preliminary studies, algal growth inhibition tests of TEMPO-CNFs were conducted using in vitro and in vivo fluorescence measurements, along with measurements of CNFs and ion concentrations in the test dispersions. The test results showed that no growth inhibition was observed on growth rate or yield even at the maximum CNF concentration of 100 mg/L, suggesting that the ecological effect of TEMPO-CNFs on algae was relatively low. The results of this study will be valuable for conducting ecotoxicity assessments on additional CNFs and comparable nanomaterials in future studies.

Hydrophilic Reduction-Resistant Spin Labels of Pyrrolidine and Pyrroline Series from 3,4-Bis-hydroxymethyl-2,2,5,5-tetraethylpyrrolidine-1-oxyl.

Highly resistant to reduction nitroxides open new opportunities for structural studies of biological macromolecules in their native environment inside living cells and for functional imaging of pH and thiols, enzymatic activity and redox status in living animals. 3,4-Disubstituted nitroxides of 2,2,5,5-tetraethylpyrrolidine and pyrroline series with a functional group for binding to biomolecules and a polar moiety for higher solubility in water and for more rigid attachment via additional coordination to polar sites were designed and synthesized. The EPR spectra, lipophilicities, kinetics of the reduction in ascorbate-containing systems and the decay rates in liver homogenates were measured. The EPR spectra of all 3,4-disubstituted pyrrolidine nitroxides showed additional large splitting on methylene hydrogens of the ethyl groups, while the spectra of similar pyrroline nitroxides were represented with a simple triplet with narrow lines and hyperfine structure of the nitrogen manifolds resolved in oxygen-free conditions. Both pyrrolidine and pyrroline nitroxides demonstrated low rates of reduction with ascorbate, pyrrolidines being a bit more stable than similar pyrrolines. The decay of positively charged nitroxides in the rat liver homogenate was faster than that of neutral and negatively charged radicals, with lipophilicity, rate of reduction with ascorbate and the ring type playing minor role. The EPR spectra of N,N-dimethyl-3,4-bis-(aminomethyl)-2,2,5,5-tetraethylpyrrolidine-1-oxyl showed dependence on pH with pKa = 3, ΔaN = 0.055 mT and ΔaH = 0.075 mT.

Enhancement of the production of TEMPO-mediated oxidation cellulose nanofibrils by kneading.

The industrial use of TEMPO-mediated oxidation (TMO) reaction to produce highly fibrillated cellulose nanofibrils has been hindered by high catalyst costs, long reaction times and high reaction volumes. The hypothesis that cellulose concentration during TMO process is key to increase the process of efficiency has been confirmed. The novelty of this research is the proof-of-concept for a significant enhancement of the TMO reaction by kneading the cellulose to work in concentrations above 120 g/L. Results show that the increase of the cellulose concentration in the TMO reaction, from the traditional 10 g/L to 120 g/L, increase not only the production for the same reaction volume (1200 %) but also the pulp recovery (up to 94 %). Moreover, the oxidation time can be reduced from 42 min to only 4 min while properties of both the oxidized pulps and the final nanocellulose are similar. On the other hand, the use of buffers in the TMO reaction allows us to keep the pH constant without using NaOH, and to improve the selectivity of the carboxyl groups production. The proposed process also minimizes the final environmental impact.

DNA-Compatible Copper/TEMPO Oxidation for DNA-Encoded Libraries.

Aldehydes are important synthons for DNA-encoded library (DEL) construction, but the development of a DNA-compatible method for the oxidation of alcohols to aldehydes remains a significant challenge in the field of DEL chemistry. We report that a copper/TEMPO catalyst system enables the solution-phase DNA-compatible oxidation of DNA-linked primary activated alcohols to aldehydes. The semiaqueous, room-temperature reaction conditions afford oxidation of benzylic, heterobenzylic, and allylic alcohols in high yield, with DNA compatibility verified by mass spectrometry, qPCR, Sanger sequencing, and ligation assays. Subsequent transformations of the resulting aldehydes demonstrate the potential of this method for robust library diversification.

Formation of free radicals in Chi-aroma Baijiu during aging process with fat pork.

Soaking aged fat pork is a special aging process in the production of Chi-aroma Baijiu considered to involve the formation of free radicals. This study aimed to investigate the free radicals' formation pathway in Chi-aroma Baijiu during aged fat pork soaking by using electron paramagnetic resonance (EPR) and spin trapping with 5,5-dimethyl-1-pyrrolin-n-oxide (DMPO). The alkyl radical adducts (DMPO-R) and hydroxyl radical adducts (DMPO-OH) were detected in Baijiu after soaking the fat pork for aging. During the preparation process of aged fat pork, alkoxy radicals adduct (DMPO-RO) were mainly detected since lipid oxidation. Oleic acid and linoleic acid, the two main unsaturated fatty acids in fat pork, produced alkoxy radicals in the oxidation process. The total amounts of spins in linoleic acid and oleic acid after 4-month oxidation treatment increased by 248.07 ± 26.65% and 34.17 ± 0.72% than 0-month. It indicated that the free radicals in aged Chi-aroma Baijiu were mainly derived from the two main unsaturated fatty acids in aged fat pork and linoleic acid had a stronger ability to produce free radicals than oleic acid. Alkoxy radicals (RO·) from fat pork reacted with ethanol in Baijiu to form alkyl radicals (R·). The peroxide bond of hydroperoxides from the oxidation of unsaturated fatty acid was cleaved to form hydroxyl radicals (·OH) that were transferred to Baijiu. The results provide theoretical guidance for the subsequent work of free radicals scavenging.