• Journal of Korea Technical Association of The Pulp and Paper Industry
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• v.47 no.2
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• pp.42-52
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• 2015

In this study, cellulose nanofibrils (CNF) were modified through carboxymethylation or TEMPO-mediated oxidation and their effects on ionicity and characteristics of sheet, film, and foam were investigated. Carboxymethylation was carried out on pulp fibers as a pre-treatment before preparation of CNF. The gel-like and translucent CNF hydrogel was obtained by grinding of carboxymethylated cellulose fibers. Carboxymethylated CNF film and freeze dried sheet showed higher transparency than that of untreated CNF. The CNF sheet with high strength and the CNF foam without large ice crystals were obtained by using the carboxymethylated CNF. TEMPO-mediated oxidation was carried out as a post-treatment of CNF. The zeta potential and charge demand of TEMPO-oxidized CNF were increased with an increase in oxidation time and addition amount of NaClO. The density of sheet made of TEMPO oxidized CNF was increased with the amount of oxidizing agent. The TEMPO oxidized cellulose nanofiber (TOCN) which was obtained from supernatant after centrifugation could be converted to transparent film.

• Korean Journal of Food Science and Technology
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• v.33 no.1
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• pp.40-44
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• 2001

The effects of TEMPO and NaBr concentration, and temperature on the selective oxidation of primary alcohol groups in corn starch were examined. Reaction time decreased with the increased levels of TEMPO, NaBr and temperature up to 1.7 mM and 100 mM per 100 mM anhydroglucose unit(AGU) and $14^{\circ}C$, respectively, and did not change appreciably at the higher levels. Yield decreased with the increased NaBr levels and was not affected TEMPO level and the temperature. NaBr level and temperature showed negative effects on the selectivity. But the selectivity was not affected by NaBr level and temperature until 100 mM/100 mM AGU and $6^{\circ}C$. TEMPO had no effect on the selectivity significantly.

• Applied Chemistry for Engineering
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• v.33 no.1
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• pp.103-108
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• 2022

This research work reports the development of a Ruthenium/2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO)/nitrate catalyst system for the highly selective transformation of isosorbide (1,4:3,6-dianhydro-D-glucitol) to isosorbide-diketone (2,6-dioxabicyclo (3,3,0)octan-4,8-one). Isosorbide is a critical platform molecule for future manufacturing processes. TEMPO has been utilized to convert alcohols to carbonyl compounds for a long time. The optimal chemical reaction condition was found to be when using isosorbide (0.5 mmol) with supported Ru (10 mol%), TEMPO (5 mol%), and sodium nitrate (0.03 mmol) in the presence of acetic acid (3 ml) as a solvent at 50 ℃ and 1 atm oxygen pressure. This catalyst system demonstrated good selectivity (> 97%) and yield (87%) with respect to the desired product, in addition to a putative catalytic double oxidation mechanism.

• Journal of the Korean Chemical Society
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• v.38 no.4
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• pp.328-332
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• 1994

• Journal of the Korean Wood Science and Technology
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• v.43 no.5
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• pp.613-627
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• 2015

Simple methods of conductometric titration and infrared spectroscopy were used to quantify the surface carboxyl content of cellulose fibrils isolated by 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-mediated oxidation. The effects of different cellulose sources, post or assisted-sonication oxidation treatment, and the amount of sodium hypochlorite addition on the carboxyl content of cellulose were reported. This study showed that post sonication treatment had no influence on the improvement of surface carboxyl charge of cellulose macrofibrils (CMFs). However, the carboxyl content increased for the isolated cellulose nanofibrils (CNFs). Thus the carboxyl content of CNFs is different from those of their corresponding bulk oxidized cellulose and CMFs. Filter paper as a CNF source imparted a higher surface charge than did hardwood bleached kraft pulp (HWBKP) and microcrystalline cellulose (MCC). It was considered that the crystallinity and microstructure of the initial cellulose affected oxidation efficiency. In addition, the carboxyl content of cellulose was successfully controlled by applying sonication treatment during the oxidation reaction and adjusting the amount of sodium hypochlorite.

• Korean Journal of Food Science and Technology
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• v.29 no.3
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• pp.446-451
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• 1997

The primary alcohol groups of four kinds of polysaccharides (com starch, rice starch, sweet potato starch, and cellulose), with different structures and water solubilities, were oxidized to carboxyl groups using 2,2,6,6-tetramethyl-1-piperidine oxoammonium ion (TEMPO) at $25^{\circ}C$. The optimum pH, TEMPO content, and NaBr content for the TEMPO/hypobromite-catalyzed oxidation of the polysaccharides were $10.5{\sim}11.0$, 10 mmol/mol primary alcohol, and 0.49 mmol/mol primary alcohol, respectively. The oxidation degree for the primary alcohol group was more than 90% for all four kinds of the polysaccharides. The oxidation process greatly increased the water solubility of the polysaccharides. Water-insoluble polysaccharide such as cellulose became water-soluble to the extent of 8.42% (w/v). And also, the polysaccharides with very low water solubility (less than 0.10% (w/v)) such as com starch, rice starch, and sweet potato starch had high water solubility of approximately 45%(w/v). The gel-forming abilities with calcium ion were determined. The oxidized polysaccharides are new anionic polymers with unique structures that could have application as gums, gels, and films.

• Journal of the Korean Chemical Society
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• v.39 no.8
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• pp.657-665
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• 1995

The oxidation of various benzyl ethers and benzyl alkyl ethers to benzoates has been studied in two-phase system of $CH_3CO_2Et$ and aqueous NaOCl (6.6 mol eq.). The oxidant N-oxo-4-methoxy-2,2,6,6-tetramethylpiperidium bromide (N-oxoammonium salt) was prepared in situ and recycled by addition of 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (0.03 mol eq., 4-methoxy-TEMPO), co-catalyst KBr (0.03mol eq.) and second oxidant NaOCl. Thus the catalytic amount of 4-methoxy-TEMPO was used. An adjustment of the pH value of below 8.0 was also required for this reaction with 2.5 hr of reaction time at 0∼5$^{\circ}C$. Under these conditions benzyl ethers were oxidized to benzoates. The selectivity of oxidation of benzyl alkyl ethers is dependent on the acidity of hydrogen and steric effect of alkyl group.

• Korean Journal of Food Science and Technology
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• v.33 no.2
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• pp.209-215
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• 2001

This study was conducted to examine the effects of 2,2,6,6-tetramethyl-1-piperidine oxoammonium ion(TEMPO) and sodium bromide(NaBr) for the selective oxidation on primary alcohol groups of rice starch molecules in rice flour and to use oxidized rice flour in Julpyun to extend its shelf life. Reaction time decreased with higher levels of TEMPO and NaBr. Yield and selectivity decreased with increased NaBr levels. TEMPO increased yield until certain levels, but decreased thereafter. The levels of TEMPO and NaBr for the preparation of oxidized rice flour were determined as 0.9 and 44 mM/100 mM anhydroglucose unit, respectively. Water and oil binding capacities, and viscosity increased significantly by the oxidation of rice flour. The partial replacement of rice flour with oxidized rice flour increased peak viscosity and decreased setback. Oxidized rice flour with the increased amount of water showed positive effect on the textural properties of Julpyun during storage.

• Bulletin of the Korean Chemical Society
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• v.35 no.3
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• pp.715-720
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• 2014

A Cu(II) complex with an three nitrogens and one sulfur coordination environment was synthesized and characterized. Its redox potential was observed at 0.483 V vs. NHE, very similar to that of a Cu-containing fungal enzyme, galactose oxidase, which catalyzes the oxidation of alcohols to corresponding aldehydes with the concomitant reduction of molecular oxygen to water. The Cu(II) complex selectively oxidizes the benzylic alcohols using TEMPO/$O_2$ under mild reaction conditions to corresponding aldehydes without forming any over-oxidation product. Moreover, the catalyst can be recovered and reused multiple times for further oxidation reactions, thus minimizing the waste generation.

• Applied Chemistry for Engineering
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• v.27 no.4
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• pp.380-385
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• 2016

Nanocelluloses, mainly cellulose nanofibrils (CNF) and cellulose nanocrystals (CNC, i.e., defect-free, rod-like crystalline residues after acid hydrolysis of fibers), have been the subject of recent interest. Due to the presence of hydroxyl groups on the surface of nanocelluloses, their surfaces are reactive, making them suitable candidates for reinforcing materials for manufacturing polymer composites. In this study, CNF was used as a reinforcing material for manufacturing cement composites. CNF was prepared by TEMPO (2,2,6,6,-tetramethyl piperidine-1-oxyl radical) oxidation procedure combined with extensive homogenization and ultrasonication. Transmission electron microscopy (TEM) analysis of the suspension showed the width of CNF between 10 and 15 nm. The compressive strength of cement composites containing 0.5% CNF was comparable to that of conventional cement composites. On the other hand, the tensile and flexural strength were improved by 49.7% and 38.8%, respectively, compared to those of conventional cement composites. Also, at an ambient condition, the degree of self-shrinkage reduction reached to 18.9% in one day, followed by 5.9% in 28 days after molding.