• Bulletin of the Korean Chemical Society
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• v.12 no.5
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• pp.537-540
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• 1991

Electrophilic methylation reactions of five-membered heteroaromatic compounds, furan, pyrrole and thiophene, with the dimethylfluoronium ion, ${CH_3}{FCH_3}(+), have been investigated theoretically by the MNDO method. The site selectivity of ${\alpha}, {\beta}$ and heteroatom (X) is related to charge density of the site, indicating that the site selectivity is dictated by electrosatic interaction between two reaction centers. The reactivity order between the three heteroaromatics can not be determined decisively since the order differs depending on which site is compared, with relatively low activation enthalpies, ${\Delta}{H^\neq}$= 20-30 kcal/mol, in all cases. These site and substrate selectivity behaviors are consistent with the gas-phase experimental results.

• Journal of Ceramic Processing Research
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• v.19 no.6
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• pp.499-503
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• 2018

In this paper, cobalt embedded in nitrogen and sulfur co-doped carbon nanotubes (CoNSTs) were synthesized for oxygen reduction reaction (ORR) catalysts. The CoNSTs were prepared through a facile heat treatment method without any templates. Different amounts of the metal salt were employed to examine the physicochemical and electrochemical properties of the CoNSTs. The CoNSTs showed the bamboo-like tube morphology with the encased Co nanoparticles in the tubes. Through the x-ray photoelectron spectroscopy analysis, the catalysts exhibited different chemical states of the nitrogen and sulfur species. As a result, the CoNST performed high activity toward the ORR in an acidic condition with the onset potential of 0.863 V (vs. reversible hydrogen electrode). It was clearly demonstrated from the electrochemical characterizations that the quality of the nitrogen and sulfur species significantly influences the ORR activity rather than the total amount of the dopants.

• Clean Technology
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• v.16 no.3
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• pp.220-228
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• 2010

Four Keggin-type heteropolyacids, $H_nXM_{12}O_{40}$(X = P and Si, M = W and Mo) that were substituted with heteroatom and polyatom were applied to the dehydration reaction of fructose to 5-hydroxymethylfurfural (HMF). The results showed that the acid became stronger when the heteroatom and polyatom were substituted with P and W than the cases of Si and Mo, respectively. However, the amount of acidic sites increased with the decrease in the acid strength, resulting in the change of the catalytic activity of heteropolyacids in the dehydration reaction. The experimental results revealed that four different heteropolyacids produced similar amounts of HMF via the dehydration reaction of fructose due to the counterbalancing effect between the amount of active sites, which is related to the catalytic activity of heteropolyacids, and the softness of polyanion. In addition, it was observed that the prepared heteropolyacids showed good structural stability after heat treatment at $200^{\circ}C$.

• Bulletin of the Korean Chemical Society
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• v.33 no.10
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• pp.3343-3348
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• 2012

The possible ways for increasing the antioxidant properties of vitamin E have been investigated with density function theory. The effect of replacing three methyl groups of vitamin E with various substituents such as electron donating and electron withdrawing groups on the antioxidant properties of vitamin E were investigated. Also the effects of the reducing the number of atoms in the heterocyclic ring and replacing the oxygen heteroatom with other heteroatoms on the antioxidant properties of vitamin E were investigated. The novel structures that obtained from replacing methyl groups with substituents such as $NH_2$, OH, COOH and NHMe have greater antioxidant activity than vitamin E. Obtained results reveal that novel structure that obtained with replacing O with NH hetroatom would be a better antioxidant than vitamin E. The results reveal that reducing the number of atoms in the heterocyclic ring is a better way to synthesize novel antioxidants.

• Korean Chemical Engineering Research
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• v.47 no.2
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• pp.163-168
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• 2009

Negative differential resistance(NDR) behaviors of Keggin-type and Wells-Dawson-type heteropolyacids with cation, heteroatom, and polyatom substitutions were investigated by scanning tunneling microscopy. A reliable correlation between NDR peak voltage and reduction potential of heteropolyacid catalysts was established. It was found that more reducible heteropolyacid catalyst showed NDR behavior at less negative voltage, regardless of the structural difference. Thus, NDR peak voltage of heteropolyacid catalyst could be utilized as a single correlating parameter for the reduction potential of heteropolyacid catalyst.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2008.06a
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• pp.465-465
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• 2008

Conjugated polymers have attracted much scientific and technological research interest during the past few decades because of their potential use such as polymer light-emitting diodes (PLEDs).1,2 Particularly, lots of phenylene-based polymers such as polyfluorene and its derivatives have been synthesized because of their high photoluminescence quantum efficiencies and thermal stabilities. However, troublesome long wavelength emission in polymer film of polyfluorenes on heating during device formation or operation has been the crucial problem for practical applications. The source of the long wavelength emission was initially believed to be solely due to excimer emission as a result of polymer aggregation. It has also recently been correlated with emissions from ketonic defects in the fluorene units. Many efforts have been made to reduce the tendency to red-shifted emission. Here, we report for the first time the design and synthesis of novel 9,9-spiro bifluornene-based polymers containing heteroatoms such as N, S in its molecular skeleton. Especially, the 9,9-spiro bifluornene-based polymers containing N atom showed stable blue electroluminescence, which did not show spectral change upon thermal annealing.

• YAKHAK HOEJI
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• v.41 no.6
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• pp.718-723
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• 1997

In the course of developing novel antitumor intercalating agents, we synthesized 3- carbamoyloxymethyl-azaanthraquinones 6-12, incorporating the latent alkylating functionality. These compounds were designed to explore the effect of heteroatom incorporation into anthraquinone chromophore and the effect of the incorporation of the latent alkylating functionality. The derivatives were prepared by hetero Diels-Alder reaction as a key step followed by functionality of allylic methyl to the desired substituents. Growth inhibitory studies of the azaanthraquinones were conducted in vitro against human cancer cell lines (SNU-354: liver and MCF7: breast) and human epidermoid carcinoma cells that are sensitive (KB-3-1) and multidrug-resistant (KB-V-1). The derivatives were 10 to 100-fold less potent than doxorubicin against sensitive cell lines. However, they were marginally cross-resistant with doxorubicin against KB-V-1.

• Bulletin of the Korean Chemical Society
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• v.21 no.9
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• pp.891-895
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• 2000

Transmission of substituent effects through 5-membered heteroaromaticrings isinvestigated theoretically at the RHF/6-31+G* and B3LYP/6-31+G* levelsusing the deprotonation equilibria of phenol analogues with heteroatoms Y = NH, O, PHand S. The incr ease in the resonance delocalization of the $\pilone-pair$ on the phe-nolic oxygen atom, $n\pi(O)$, accompanied with the deprotonation depends on the heteroatom Y,in the order NH < O < PH < S. This represents the $\pielectron$ accepting ability, or conversely reverse order of the $\pielectron$ donating ability of the $\pilone-pair$ on Y, $n\pi(Y).$ The transmission efficiency of substituenteffects is, however,in the reverse order NH > O > S, which represents the order of delocalizability of $n\pi(Y).$ A better correlation is obtained with ${\sigma}p$ - than with ${\sigma}p$ for the Hammett type plots with the positive slope, $\rho-$ > 0, of the magnitude in the same order as that for the delocalizability of $n\pi(Y).$ Thedeprotonation energy, ΔG = [G(PA) + G(H+)] -G(P), decreases with the increasein the extence delocalization in the order NH > O > PH > S.

• Journal of the Korean institute of surface engineering
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• v.51 no.5
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• pp.332-336
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• 2018

Alkaline oxygen electrocatalysis, targeting anion exchange membrane alkaline-based metal-air batteries has become a subject of intensive investigation because of its advantages compared to its acidic counterparts in reaction kinetics and materials stability. However, significant breakthroughs in the design and synthesis of efficient oxygen reduction catalysts from earth-abundant elements instead of precious metals in alkaline media still remain in high demand. One of the most inexpensive alternatives is carbonaceous materials, which have attracted extensive attention either as catalyst supports or as metal-free cathode catalysts for oxygen reduction. Also, carbon composite materials have been recognized as the most promising because of their reasonable balance between catalytic activity, durability, and cost. In particular, heteroatom (e.g., N, B, S or P) doping on carbon materials can tune the electronic and geometric properties of carbon, providing more active sites and enhancing the interaction between carbon structure and active sites. Here, we focused on boron and nitrogen doped nanocarbon composit (BNC nanocarbon) catalysts synthesized by a solution plasma process using the simple precursor of pyridine and boric acid without further annealing process. Additionally, guidance for rational design and synthesis of alkaline ORR catalysts with improved activity is also presented.

• Membrane Journal
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• v.29 no.4
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• pp.202-215
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• 2019

Molecular sieve membranes separate molecules based on their size and/or shape and have been of high interest, due to their potentially high energy efficiency and high selectivity. Zeolite MFI membrane is one of the most-studied molecular sieve membranes and has affected following studies on other molecular sieve membranes. This review discusses the technical developments on the control of morphology, microstructure, and defect of MFI membranes, which have significantly improved xylene isomer separation performances. These include crystal morphology control, effective secondary growth, seed coating method, crystal orientation control, heteroatom doping, and defect healing method.