• Bulletin of the Korean Chemical Society
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• v.33 no.10
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• pp.3196-3202
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• 2012

Post-synthesis is used to synthesize organic hybrid inorganic mesoporous sieves. In this method, the activity and structure of the base sieve are crucial to obtain the definable hybrid materials. The chemical and physical properties of the base can be largely changed either by the final step of its synthesizing processes, by template removal which is accomplished with the oxidative thermal decomposition (burning) method or by solvent extraction method. In this paper we compared two methods for the post-synthesis of organic hybrid MCM-48. When the template was extracted with HCl/alcohol mixture, the final product showed larger pore size, larger pore volume and better crystallinity compared to the case of the thermal decomposition. The reactivity of the surface silanol group of template free MCM-48 was also checked with an alkylsilylation reagent $CH_2=CHSi(OC_2H_5)_3$. Raman and $^{29}Si$ NMR spectra of MCM-48 in the test reaction indicated that more of the organic group was grafted to the surface of the sample after the template was removed with the solvent extraction method. Direct synthesis of vinyl-MCM-48 was also investigated and its characteristics were compared with the case of post-synthesis. From the results, it was suggested that the structure and chemical reactivity can be maintained in the solvent extraction method and that organic grafting after the solvent extraction can be a good candidate to synthesize a definable hybrid porous material.

• Journal of the Korean Chemical Society
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• v.40 no.10
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• pp.670-673
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• 1996

• Korean Chemical Engineering Research
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• v.50 no.5
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• pp.843-849
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• 2012

When we use NiO based particle as an oxygen carrier in a chemical looping combustion system, the fuel conversion and the $CO_2$ selectivity decreased with increasing reaction temperature within high temperature range (> $900^{\circ}C$) due to the increment of exhaust CO concentration from reduction reactor. To improve reduction reactivity at high temperature, the applicable metal oxide component was selected by calculation of the equilibrium CO concentration of metal oxide components. After that, feasibility of reduction reactivity improvement at high temperature was checked by using solid mixture of the selected metal oxide particle and NiO based oxygen carrier. The reactivity was measured and investigated using batch type fluidized bed. The solid mixture of $Co_3O_4/CoAl_2O_4$(10%) and OCN706-1100(90%) showed higher fuel conversion, higher $CO_2$ selectivity and lower CO concentration than OCN706-1100(100%) cases. Consequently, we could conclude that improvement of reduction reactivity at high temperature range by adding some $Co_3O_4$ based oxygen carrier was feasible.

• Journal of Korean Society for Atmospheric Environment
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• v.16 no.4
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• pp.389-398
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• 2000

Photocatalytic removal of benzene from air was examined using titanium dioxide photocatalyst films prepared on soda lime glass(50$\times$50$\times$2 mm) by spin coating and chemical vapor deposition. For the measurement of photocatalytic reactivity titanium dioxide coated glass was placed into a batch reactor and concentration of benzene in the reactor was set to abuot 100 ppm, and then illuminated with UV. It was found that catalytic reactivity of titanium dioxide films increased with the increase of titanium dioxide film thickness and then level off beyond a certain film thickness. UV absorption by the films showed the similar trend. The formation of stoichiometric amount of carbon dioxide was confirmed by measurement of carbon dioxide concentration in the reactor. In general spin coated films revealed better photocatalytic reactivity than chemically deposited one within the experimental ranges covered in this study. Morphology and crystal structure of prepared films were investigated by XRD and SEM and they showed significant difference between spin coated films and CVD films. Highest quantum efficiency of prepared titanium dioxide photocatalyst was close to 50%.

• Journal of the Korean Chemical Society
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• v.25 no.3
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• pp.145-151
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• 1981

The intrinsic reactivity of $S_N2$reaction in the gas phase was discussed MO theoretically (CNDO/2). We investigated the changes in geometry and electronic structure by means of the partial geometry optimization for reactantes, transition states, and products with various nucleophiles and leaving groups. We found that it was possible to discuss qualitatively the reactivity of $S_N2$ reaction with CNDO/2 MO calculation and the reactivity was controlled by basicity and of induced polarizability.

• Journal of the Korean Chemical Society
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• v.25 no.3
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• pp.140-144
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• 1981

The structure and reactivity of isophorone diisocyanate, which is used as a curing agent in propellants casting, were investigated using the EHT, CNDO/2 and STO-3G MO methods. The results showed that the reactivity can be assessed by the positive charge on C atom of -NCO group. The structure of this compound was found to be such that it has slow polymerization rate but provides homogenous matrix for explosives.

• Bulletin of the Korean Chemical Society
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• v.35 no.2
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• pp.546-550
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• 2014

Relative reactivity of various carbonyl and acid derivatives in MPV-type (Meerwein-Ponndorf-Verley) reduction with an DIBAL(F) model has been studied via DFT and MP2 methods. Free energies of initial adduct formation (-Gadd) of DIBAL(F) model and carbonyls are in the order of amide < ester < aldehyde < ketone < acid chloride; in the alan-amide adduct, the developed positive charge at carbonyl carbon is expected to be stabilized by amide resonance, but in the acid chloride adduct it is destabilized by inductive effect of chloride. However the TS barrier energies (${\Delta}G_{TS}$) for the MPV-type hydride reduction of the carbonyl adducts are in the order of aldehyde < ketone < acid chloride << ester < amide; presumably decreasing order of electrophilicity of carbonyl carbon at adducts, which is well correlated with experimental data. It is noted that the relative reactivity of carbonyl derivatives in MPV-type reduction with DIBAL(X) is not governed by the alan-adduct formation energies, but follows the order of electrophilicity of carbonyl carbon of transition states.

• Journal of the Korean Chemical Society
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• v.18 no.1
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• pp.3-7
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• 1974

Extended Huckel calculations have been carried out to study the effect of sulfenyl, sulfinyl and sulfonyl groups on the reactivity of halides in $S-N2$ reactions. Results indicate that the most reasonable reactivity index is that based on the Frontier electron for the bond formation process.

• Bulletin of the Korean Chemical Society
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• v.13 no.1
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• pp.32-36
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• 1992

The gas-phase pyrolysis reactions of 2-alkoxypyrimidines(II), 2-alkoxypyrazines(III), 4-ethoxypyrimidine(IV) and 3-ethoxypyridazine(V) are investigated theoretically using the AM1 MO method. These compounds pyrolyze in a concerted retro-ene process with a six-membered cyclic transition state (TS). The relative order of reactivity if (IV)>(II)>(III)>(V), which can be rationalized by the two effects arising from electron-withdrawing power of the aza-substituent: (ⅰ) Electron withdrawal from the C-O bond accelerates the rate and (ⅱ) electron withdrawal from the $N^1$-atom, that is participating in the six-membered TS, deactivates the reaction. We are unable to explain the experimental result of the greatest reactivity for pyridazine, (V), with our AM1 results. The reactivity increase accompanied by successive methylation of the ethoxy group, ethoxytert-butoxy, is due to a release of steric crowding in the activation process.

• Bulletin of the Korean Chemical Society
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• v.9 no.6
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• pp.394-398
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• 1988

Unusually high reactivity was found in peptide bond formation between p-nitrobenzophenone oxime resin (I) ester and amino acid 4-(methylthio)phentyl (MTP) esters. A charge-transfer complex between the two phenyl rings of the oxime resin (I) and the incoming amino acid MTP esters was considered to be responsible to accelerate the aminolysis reaction of the peptide oxime resin ester. Several di-, tri-, and pentapeptide fragments for preparing enkephalin and glutathione oligomers were successfully prepared in short times.