• Bulletin of the Korean Chemical Society
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• v.15 no.10
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• pp.881-888
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• 1994

The approximate rates and stoichiometry of the reaction of excess sodium tris(diethylamino)aluminum hydride (ST-DEA) with selected organic compounds containing representative functional groups under standardized conditions(tetrahydrofuran, $0{\circ}$) were studied in order to characterize the reducing characteristics of the reagent for selective reductions. The reducing ability of STDEA was also compared with those of the parent sodium aluminum hydride (SAH) and lithium tris(diethylamino)aluminum hydride (LTDEA). The reagent appears to be milder than LTDEA. Nevertheless, the reducing action of STDEA is very similar to that observed previously for LTDEA, as is the case of the corresponding parent sodium and lithium aluminum hydrides. STDEA shows a unique reducing characteristics. Thus, benzyl alcohol, phenol and 1-hexanol evolved hydrogen slowly, whereas 3-hexanol and 3-ethyl-3-pentanol, secondary and tertiary alcohols, were essentially inert to STDEA. Primary amine, such as n-hexylamine, evolved only 1 equivalent of hydrogen slowly. On the other hand, thiols examined were absolutely stable. STDEA reduced aidehydes and ketones rapidly to the corresponding alcohols. The stereoselectivity in the reduction of cyclic ketones by STDEA was similar to that by LTDEA. Quinones, such as p-benzoquinone and anthraquinone, were reduced to the corresponding 1,4-dihydroxycyclohexadienes without evolution of hydrogen. Carboxylic acids and anhydrides were reduced very slowly, whereas acid chlorides were reduced to the corresponding alcohols readily. Esters and epoxides were also reduced readily. Primary carboxamides consumed hydrides for reduction slowly with concurrent hydrogen evolution, but tertiary amides were readily reduced to the corresponding tertiary amines. The rate of reduction of aromatic nitriles was much faster than that of aliphatic nitriles. Nitrogen compounds examined were also reduced slowly. Finally, disulfide, sulfoxide, sulfone, and cyclohexyl tosylate were readily reduced without evolution of hydrogen. In addition to that, the reagent appears to be an excellent partial reducing agent: like LTDEA, STDEA converted ester and primary carboxamides to the corresponding aldehydes in good yields. Furthermore, the reagent reduced aromatic nitriles to the corresponding aldehydes chemoselectively in the presence of aliphatic nitriles. Consequently, STDEA can replace LTDEA effectively, with a higher selectivity, in most organic reductions.

• Bulletin of the Korean Chemical Society
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• v.13 no.5
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• pp.531-537
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• 1992

The approximate rates and stoichiometry of the reaction of excess potassium 2-thexyl-1,3,2-dioxaborinane hydride(KTDBNH) with 55 selected compounds containing representative functional groups under standardized conditions (tetrahydrofuran, TEX>$0^{\circ}C$, reagent : compound=4 : 1) was examined in order to define the characteristics of the reagent for selective reductions. Benzyl alcohol and phenol evolve hydrogen immediately. However, primary, secondary and tertiary alcohols evolve hydrogen slowly, and the rate of hydrogen evolution is in order of $1^{\circ}$> $2^{\circ}$> $3^{\circ}$. n-Hexylamine is inert toward the reagent, whereas the thiols examined evolve hydrogen rapidly. Aldehydes and ketones are reduced rapidly and quantitatively to give the corresponding alcohols. Cinnamaldehyde is rapidly reduced to cinnamyl alcohol, and further reduction is slow under these conditions. The reaction with p-benzoquinone dose not show a clean reduction, but anthraquinone is cleanly reduced to 9,10-dihydro-9,10-anthracenediol. Carboxylic acids liberate hydrogen immediately, further reduction is very slow. Cyclic anhydrides slowly consume 2 equiv of hydride, corresponding to reduction to the caboxylic acid and alcohol stages. Acid chlorides, esters, and lactones are rapidly and quantitatively reduced to the corresponding carbinols. Epoxides consume 1 equiv hydride slowly. Primary amides evolve 1 equiv of hydrogen readily, but further reduction is slow. Tertiary amides are also reduced slowly. Both aliphatic and aromatic nitriles consume 1 equiv of hydride rapidly, but further hydride uptake is slow. Analysis of the reaction mixture with 2,4-dinitrophenylhydrazine yields 64% of caproaldehyde and 87% of benzaldehyde, respectively. 1-Nitropropane utilizes 2 equiv of hydride, one for hydrogen evolution and the other for reduction. Other nitrogen compounds examined are also reduced slowly. Cyclohexanone oxime undergoes slow reduction to N-cyclohexylhydroxyamine. Pyridine ring is slowly attacked. Disulfides examined are reduced readily to the correponding thiols with rapid evolution of 1 equiv hydrogen. Dimethyl sulfoxide is reduced slowly to dimethyl sulfide, whereas the reduction of diphenyl sulfone is very slow. Sulfonic acids only liberate hydrogen quantitatively without any reduction. Finally, cyclohexyl tosylate is inert to this reagent. Consequently, potassium 2-thexyl-1,3,2-dioxaborinane hydride, a monoalkyldialkoxyborohydride, shows a unique reducing characteristics. The reducing power of this reagent exists somewhere between trialkylborohydrides and trialkoxyborohydride. Therefore, the reagent should find a useful application in organic synthesis, especially in the field of selective reduction.

• Membrane Journal
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• v.29 no.3
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• pp.183-189
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• 2019

Amphiphilic PCZ-r-PEG random copolymer assisted solvothermal process is used to prepare mesoporous $TiO_2$ microspheres generated from nanoparticles by self-assembly method. Synthesized PCZ-r-PEG is characterized by Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR), gel permeation chromatography (GPC) and transmission electron microscopy (TEM). The mesoporous $TiO_2$ are prepared by PCZ-r-PEG, glucose, water in tertrahydrofuran solution at $150^{\circ}C$ for 12 h and the $TiO_2$ microspheres are calcined at $550^{\circ}C$ for 30 min to further crystallize and organic residue are removed. Morphology and crystallization phase is characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) respectively. The mesoporous $TiO_2$ crystallized in pure anatase phase with diameter of $300{\pm}20nm$.

• Journal of Korean Society of Occupational and Environmental Hygiene
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• v.29 no.1
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• pp.1-12
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• 2019

Objective: Significant concerns have been raised over chemical exposure and potential health risks such as increased cancer mortality among laboratory workers. The aim of this study was to investigate the overall exposure and unit task exposure levels of researchers in organic synthesis laboratories at universities. Methods: Seventy-seven personal Time-weighted average(TWA) samples and 139 task-based samples from four organic synthesis laboratories at two universities were collected over three days. The concentrations of acetone, chloroform, dichloromethane(DCM), diethyl ether, ethyl acetate, n-hexane, tetrahydrofuran(THF), benzene, toluene, and xylene were determined using the GC-FID. Results: The most frequently used chemicals in the laboratories were acetone, DCM, n-hexane, methanol, and THF. Carcinogens such as benzene, chloroform, and DCM were used in one or more laboratories. The TWA full-shift exposures of researchers to acetone was the highest(ND-59.3 ppm). Benzene was observed above the occupational exposure limit in 18-40% of the samples. The levels of exposure to organic solvents were statistically different by task(p<0.05), while washing task was the highest. Washing was not perceived as a part of the real lab tasks. Rather it was considered as simple dish-washing or experimental preparation and performed in an open sink where exposure to organic solvents was unavoidable. TWAs and task-based concentrations were compared by substance, which suggests that TWA-based assessment could not reflect short-term and high concentration exposures. Conclusions: Laboratory workers may be exposed to various organic solvents at levels of concern. TWA-based measurement alone cannot guarantee holistic exposure assessment among lab workers as their exposures are very dependent on their tasks. Further investigation and characterization for specific tasks and overall chronic exposures will help protect lab workers from unnecessary exposure to chemicals while they perform research.

• Korean Journal of Metals and Materials
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• v.49 no.1
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• pp.79-84
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• 2011

Double-walled carbon nanotubes (DWCNTs) with high purity were produced by the catalytic decomposition of tetrahydrofuran (THF) using a Fe-Mo/MgO catalyst at $800^{\circ}C$. The as-synthesized DWCNTs typically have catalytic impurities and amorphous carbon, which were removed by a two-step purification process consisting of acid treatment and oxidation. In the acid treatment, metallic catalysts were removed in HCl at room temperature for 5 hr with magnetic stirring. Subsequently, the oxidation, using air at $380^{\circ}C$ for 5 hr in the a vertical-type furnace, was used to remove the amorphous carbon particles. The DWCNT suspension was prepared by dispersing the purified DWCNTs in the aqueous sodium dodecyl sulfate solution with horn-type sonication. This was then air-sprayed on ITO glass to fabricate DWCNT field emitters. The field emission properties of DWCNT films related to transmittance were studied. This study provides the possibility of the application of large-area transparent CNT field emission cathodes.

• Analytical Science and Technology
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• v.20 no.5
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• pp.442-447
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• 2007

The properties of garlic (Allium sativum L.) are attributed to organosulfur compounds. In this paper, an analytical technique with a rapid and simple sample preparation procedures for determination of diallyl disulfide (DADS) in garlic was reported. The DADS was simply extracted with various solvents (methanol, benzene or tetrahydrofuran) from garlic and prepared for HPLC analysis. From the results, the methanol was select as an optimal extraction solvent. The mobile phase was composed from methanol and water, and the gradient elution mode was applied. 0.61 mg of DADS per g garlic powder can be extracted with methanol. This work offers some advantages over the currently accepted techniques and would be useful for chemical and biological studies of garlic and its products.

• Applied Chemistry for Engineering
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• v.22 no.1
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• pp.15-20
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• 2011

Poly[2,3-dimethyl-5,8-dithiophene-2-yl-quinoxaline-alt-9,9-dihexyl-9H-fluorene] (PFTQT) and poly[2,3-dimethyl-5,8-dithiophen-2-yl-quinoxaline-alt-10-hexyl-10H-phenothiazine (PPTTQT) based on 2,3-dimethyl-5,8-dithiophen-2-yl-quinoxaline weresynthesized by Suzuki coupling reaction. All polymers were soluble in common organic solvents such as chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran (THF) and toluene. The maximum absorption wavelength and band gap of PFTQT were 440 nm and 2.30 eV, and PPTTQT were 445 nm and 2.23 eV, respectively. The HOMO and LUMO energy level of PFTQT were -6.05 and -3.75 eV, and PPTTQT were -5,89 and -3.66 eV, respectively. The organic photovoltaic devices based on the blend of polymer and PCBM (1 : 2 by weight ratio) were fabricated. Efficiencies of devices were 0.24% (PFTQT) and 0.16% (PPTTQT), respectively. The short circuit current density ($J_{sc}$), fill factor (FF), and open circuit voltage ($V_{oc}$) of the device with PFTQT were $0.97mA/cm^2$, 29% and 0.86 V, and the device based on PPTTQT were $0.80mA/cm^2$, 28% and 0.71 V, 31% and 0.71 V, respectively, under air mass (AM) 1.5 G and 1 sun condition ($100mA/cm^2$).

• Applied Chemistry for Engineering
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• v.17 no.2
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• pp.223-228
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• 2006

Pore-size controlled porous carbons for the catalyst supports of the direct methanol fuel cell were prepared from the mesophase pitch by using the silica spheres with different sizes. Pitch solution in THF and spheres were mixed, carbonized and etched by 5 M NaOH to make porous carbon. Specific surface area of the porous carbons was $14.7{\sim}87.7m^2/g$ and average pore diameter was 50~550 nm which were dependent on the size of silica spheres. Aqueous reduction method was used to load 60 wt% PtRu on the prepared porous carbon supports. The electro-oxidation activity of the supported 60 wt% Pt-Ru catalysts was measured by cyclic voltammetry and unit cell test. For the 60 wt% Pt-Ru/porous carbon synthesized by 50 nm silica, current density value in the cyclic voltammetry test was $123mA/cm^2$ at 0.4 V and peak power density in the unit cell test were 105 and $162mW/cm^2$ under oxygen at 60 and $80^{\circ}C$, respectively.

• Korean Journal of Food Science and Technology
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• v.42 no.3
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• pp.257-262
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• 2010

Patulin, a secondary metabolite of mold, is commonly found in rotten apples. Many countries regulate patulin at levels ranging from 30 to $50\;{\mu}g/L$. Most analytical methods for removing patulin from apple juice include liquid-liquid extraction (LLE), which is time and labor intensive. To replace the LLE method, a solid-phase extraction (SPE) method has been developed for apple juice and unfiltered apple juice. A portion of the test sample was applied to a macroporous copolymer cartridge and washed with 5 mL of 1% sodium bicarbonate, followed by 5 mL of 1% acetic acid. Patulin was eluted with 5 mL of 2% acetonitrile in anhydrous ethyl ether. The mobile phase was tetrahydrofuran in water (0.8:99.2) and was detected with a UV detector at 276 nm. Recoveries ranged from 95 to 101% in test samples, and the minimum detectable level was 30 ppb. Because this SPE method is fast, easy, reliable, and inexpensive, it could be applicable for companies or analytical agencies to analyze patulin concentrations in apple juice.

• Journal of the Korean Chemical Society
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• v.31 no.3
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• pp.258-270
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• 1987

A series of new thorium nitrate complexes with crown ethers have been synthesized from the reaction of the hydrated thorium nitrate, with the appropriate crown ethers of different cavity sizes in various solvents such as methanol, ethanol, butanol, methylacetate, acetone, tetrahydrofuran and acetylacetone. CHN elemental analysis, ICPAS, thermal analysis and Karl-Fischer method have been used to characterize their compositions, and the spectroscopic methods of IR, UV, $^1H-NMR$, and X-ray diffraction have been employed to determine the structures and solvolysis phenomena of these complexes. and the electrical conductances were measured in DMSO, and water solvent. The solvolysis have been observed only in the complexes synthesized in acetylacetone solvent. In the solvated complexes of 15-crown-5 and 18-crown-6, the mole ratio of $Th^{4+}$: ligand : acetylacetone is found to be 1:1:1, but in the non-solvated complexes of 12-crown-4 and 15-crown-5, the mole ratios of Th:L are 1:2 and 2:3, respectively, and that in the complexes of both 18-crown-6 and dicyclohexano-18-crown-6 is 1:1. All complexes which were not solvated have shown $n{\to}{\sigma}^{\ast}$ electronic transitions of crown ether whereas complexes solvated have exhibited both $n{\to}{\sigma}^{\ast}$ of crown ether and $n{\to}{\pi}^{\ast}$ transitions of acac. The dissociation mole ratio of $Th^{4+}$ and nitrate ion is found to be 1:1 in aprotic solvent, and 1:4 in protic solvent like water.