• Bulletin of the Korean Chemical Society
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• v.26 no.4
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• pp.515-522
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• 2005

Enzyme-metal combo catalysis is described as a useful methodology for the synthesis of optically active compounds. The key point of the method is the use of enzyme and metal in combination as the catalysts for the complete transformation of racemic substrates to single enantiomeric products through dynamic kinetic resolution (DKR). In this approach, enzyme acts as an enantioselective resolving catalyst and metal does as a racemizing catalyst for the efficient DKR. Three kinds of enzyme-metal combinations - lipase-ruthenium, subtilisin-ruthenium, and lipase-palladium –have been developed as the catalysts for the DKRs of racemic alcohols, esters, and amines. The scope of the combination catalysts can be extended to the asymmetric transformations of ketones, enol acetates, and ketoximes via the DKRs. In most cases studied, enzyme-metal combo catalysis provided enantiomerically-enriched products in high yields.

• Nuclear Engineering and Technology
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• v.9 no.4
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• pp.211-222
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• 1977

The decomposition of all the individual chemicals used in the Harwell inactive vitrification pilot plant has been studied by means of a thermal balance. Weight loss curves to 110$0^{\circ}C$ have been obtained. The four materials (sodium nitrate, cesium nitrate, lithium nitrate and ruthenium nitroso-nitrate solution) showed a greater weight loss than that based on an oxide yield, and hence these compounds of their products of decomposition are volatile below 110$0^{\circ}C$. The remaining materials suffered a weight loss no more than that corresponding to a full yield of the oxide, and hence they were not volatile below 110$0^{\circ}C$. Most of chemicals begin to decompose at less than 75$^{\circ}C$ but the nitrates of cesium, strontium, barium and sodium not until 295$^{\circ}C$ to 59$0^{\circ}C$. The results obtained can be used in the analysis of process conditions in the vitrification and calcination of highly radioactive wastes and also of the thermal decomposition behaviour of mixtures containing those materials.

• Journal of the Korean Chemical Society
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• v.37 no.11
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• pp.967-973
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• 1993

${\alpha},{\omega}$-Diols such as 1,6-hexanediol and 1,7-heptanediol react with secondary amines in the presence of catalytic amount of ruthenium complex at 180$^{\circ}$C for 24 hrs to give the corresponding diamino compounds in good yields. The yield of diamino compound was affected by the molar ratio of ${\alpha},{\omega}$-diol to secondary amine. The reaction was also affected by the nature of the phosphorus ligands employed. On the other hand, aromatic primary amines react with 1,2,6-hexanetriol in the presence of RuCl_3{\cdot}H_2O-3PPh_3$ at 180$^{\circ}$C for 3 hours under argon atmosphere to give selectively 1-substituted aryl-3-hydroxyperhydroazepines in good yields. Selective synthesis of these products show that two primary hydroxy groups (1,6-positions) oxidize predominantly than secondary hydroxy group (2-position) by ruthenium-phosphorus complex. The yields were decreased according to the order of para-, meta- and ortho-substituent.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.76.2-76.2
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• 2013

Advanced electronic application areas have strongly required new materials due to the continuous shrinking dimensions of their devices. Specially, the development and use of metal precursors for atomic layer deposition has been extensively focused on application to electronic devices. Thus the systematic design and synthesis of metal compounds with relevant chemical and physical properties, such as stability, volatility, and resistance to air and moisture are very important in the vacuum deposition fields. In many case, organic ligands for metal precursors are especially focused in the related research areas because the large scale synthesis of the metal complexes with excellent properties exclusively depends on the potential usefulness of the ligands. It is recommended for metal complexes to be in monomeric forms because mononuclear complexes generally show high vapor pressures comparing with their oligomeric structure such as dimer and trimer. Simple metal alkoxides complexes are involatile except several examples such as Ti(OiPr)4, Si(OEt)4, and Hf(OtBu)4. Thus the coordinated atom of alkoxide ligands should be crowded in its own environment with some substituents by prohibiting the coordinated atoms from bonding to another metal through oxygen-bridging configuration. Alkoxide ligands containing donor-functionalized group such as amino and alkoxy which can induce the increasing of the coordinative saturation of the metal complexes and the decreasing of the intermolecular interaction between or among the metal compounds. In this presentation, we will discuss the development of metal compounds which adopted donor-functionalized alkoxide ligands derived from their alcohols for electronic application. Some recent results on ALD using metal precursors such as tin, nickel, ruthenium, and tungsten developed in our group will be disclosed.

• Analytical Science and Technology
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• v.10 no.4
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• pp.264-273
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• 1997

Anodic oxidation reaction was applied to remove trihalomethanes in an aqueous solution. Each component was determined by using solid phase microextraction(SPME) fiber and GC-ECD. Anodic and cathodic compartments were separated in order to protect contaminants and connected by $KNO_3$-agar bridge. The calibration graphs of the 6 THM components were shown good linearlity from a few ppb up to a few hundreds ppb concentration level. Anodes such as platinum(Pt), titanium(Ti). zircornium(Zr), titanium metal coated with iridium(Ti-Ir), and glassy carbon coated with mixed valence ruthenium(mv Ru) were tried to remove the THMs at different potentials. The best result was obtained on the Ti-Ir anode applied 9 volts DC. The electrode could effectively remove almost all the THM components from the stirring solution within about 1.5 hours. The glassy carbon electrode coated with mixed valence ruthenium showed excellent removing effect at the begining, but the maximum removing level was remained at 60% probably due to the destruction of the electrode surface. The concentration of chloroform, however, tends to be increased due to the electrode reaction producing the component at the condition.

• Journal of the Korean Applied Science and Technology
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• v.22 no.4
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• pp.349-354
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• 2005

It is interesting to discover the reaction kinetics of the newly developed molybdenum containing catalysts. The dissociation/adsorption of nitrogen on molybdenum surface is known to be structure sensitive, which is similar to that of nitrogen on iron surface. The rates over molybdenum nitride catalysts are increased with the increase of total pressure. This tendency is the same as that for iron catalyst, but is quite different from that for ruthenium catalyst. The activation energies of the molybdenum nitride catalysts are almost on the same level, although the activity is changed by the addition of the second component. The reaction rate is expressed as a function of the concentration of reactants and products. The surface nature of $CO_3Mo_3N$ is drastically changed by the addition of alkali, changing the main adsorbed species from $NH_2$ to NH on the surface. The strength of $NH_x$ adsorption is found to be changed by alkali dopping.

• Korean Journal of Metals and Materials
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• v.49 no.5
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• pp.395-399
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• 2011

In this study, micro gas sensors for ammonia gas were prepared by adopting MEMS technology and using a sol-gel process. Three types of sensors were prepared via different synthesis routes starting with W sol and Ru sol mixture. This mixture was deposited on a MEMS platform and the platform was subsegueny heated to a temperature of $350^{\circ}C$. The topography and crystal structure of the sensing film were studied using FE-SEM and XRD. The response of the gas sensor to $NH_3$ gas was examined at various operating temperatures and gas concentrations. The sensor response increased almost linearly with gas concentration and the best sensing response was obtained at $333^{\circ}C$ for 5.0 ppm $NH_3$ for the specimen prepared by coating $WO_3$ powders with the Ru sol mixture.

• Clean Technology
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• v.29 no.2
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• pp.79-86
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• 2023

The homogeneous catalyst, Ru-MACHO-BH, selectively performs hydrogenation reactions only on the carbonyl group of α, β-unsaturated aldehyde compounds with extremely high reactivity and selectivity. However, the hydrogenation of α, β-unsaturated aldehydes involves a heterogeneous Diels-Alder reaction, resulting in the formation of significant amounts of byproducts, such as dimers. In this study, we used the Ru-MACHO-BH catalyst (Carbonyl hydrido (tetrahydroborato) [bis (2-diphenyl phosphino ethyl) amino] ruthenium(II)) to selectively hydrogenate the carbonyl group of a specific type of α, β-unsaturated aldehyde called methacryl aldehyde, leading to the synthesis of methallyl alcohol. Simultaneously, we applied diols to inhibit the formation of byproducts. The results demonstrate that monoethylene glycol can significantly reduce the formation of diols. Based on these results, we effectively suppressed the formation of dimers containing vinyl groups in methacryl aldehyde by using hydroquinone, which can efficiently inhibit the chemical interaction of vinyl groups. Consequently, the conversion rate of methacryl aldehyde was increased. Ultimately, by reducing the amount of the expensive homogeneous catalyst Ru-MACHO-BH to 1/10, we achieved a selectivity of over 90% and a yield of over 80% for the desired product, methallyl alcohol. These results provide a method to minimize yield reduction while reducing the usage of expensive catalysts, thereby improving cost-effectiveness. We expect that the reaction could be applied to various kinds of selective hydrogenation and has been successfully run on an industrial scale.

• Journal of the Korean Chemical Society
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• v.55 no.3
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• pp.418-429
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• 2011

Novel chromium(III), manganese(II), iron(III), cobalt(II), nickel(II), copper(II), ruthenium(III), and zirconyl(II) complexes of $N^1,N^2$-bis(3-((3-hydroxynaphthalen-2-yl)methylene-amino)propyl)phthalamide ($H_4L$, 1) have been synthesized and characterized by elemental, physical, and spectral analyses. The spectral data showed that the ligand behaves as either neutral tridentate ligand as in complexes 2-5 with the general formula $[H_4LMX_2(H_2O)]{\cdot}nH_2O$ (M=Cu(II), Ni(II), Co(II), X = Cl or $NO_3$), neutral hexadentate ligand as in complexes 10-12 with the general formula $[H_4LM_2Cl_6]{\cdot}nH_2O$ (M=Fe(III), Cr(III) or Ru(III)), or dibasic hexadentate ligand as in complexes 6-9 with the general formula $[H_2LM_2Cl_2(H_2O)_4]{\cdot}nH_2O$ (M = Cu(II), Ni(II), Co(II) or Mn(II), and 13 with general formula $[H_4L(ZrO)_2Cl_2]{\cdot}8H_2O$. Molar conductance in DMF solution indicated the non-ionic nature of the complexes. The ESR spectra of solid copper(II) complexes 2, 5, and 6 showed $g_{\parallel}$ >g> $g_e$, indicating distorted octahedral structure and the presence of the unpaired electron in the $N^1,N^2$ orbital with significant covalent bond character. For the dimeric copper(II) complex $[H_2LCu_2Cl_2(H_2O)_4]{\cdot}3H_2O$ (6), the distance between the two copper centers was calculated using field zero splitting parameter for the parallel component that was estimated from the ESR spectrum. The antibacterial and antifungal activities of the compounds showed that, some of metal complexes exhibited a greater inhibitory effect than standard drug as tetracycline (bacteria) and Amphotricene B (fungi).