• Archives of Pharmacal Research
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• v.29 no.7
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• pp.563-565
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• 2006

Potential anti-Helicobacter pylori agent dehydrodiconiferyl alcohol was synthesized in 44% overall yield, starting from vanillin which could be commercially available. Carbon extension of vanillin followed by the Horner-Wadsworth-Emmons reaction, a biomolecular radical coupling reaction and DIBAL-H reduction gave dehydrodiconiferyl alcohol.

• Macromolecular Research
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• v.15 no.1
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• pp.31-38
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• 2007

Pentamethylcyclopentadienyltitanium trichloride, bis(cyclopentadienyl)titanium dichloride ($Cp_2TiCl_2$), and bis(pentamethylcyclopentadienyl)titanium dichloride were used in the polymerization of styrene without the aid of Group I-III cocatalysts. The properties of the resulting polymer indicated that polymerization was more controlled than in thermal polymerization. The kinetic studies indicated that a lower level of termination is present and that the polymer chain can be extended by adding an additional monomer. To elucidate the mechanism of polymerization, a series of experiments was performed. All results supported the involvement of a radical mechanism in the polymerization using $Cp_2TiCl_2$. The possibility of atom transfer radical polymerization (ATRP) mechanism was investigated by isolating the intermediate species. We could confirm the activation step from the reaction of 1-PEC1 with $Cp_2TiCl$ by detecting the coupling product of the generated active radicals. However, the reversible deactivation reaction competes with other side reactions, and it detection was difficult with our model system.

• Macromolecular Research
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• v.15 no.6
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• pp.541-546
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• 2007

The combination of atom transfer radical polymerization (ATRP) and click chemistry was employed for the efficient preparation of well-defined block copolymers. Bromo terminated poly(methyl acrylate) (pMA-Br) was prepared by an ATRP initiator, ethyl-2-bromoisobutyrate (EBiB). Subsequently, the bromine chain end of pMA-Br was converted to an azide group by simple nucleophilic substitution reaction. ${\alpha}-Alkyn-{\omega}-bromo-functionalized$ polystyrene was also synthesized by ATRP using the alkyn-functionalized initiator, propargyl-2-bromoisobutyrate (PgBiB). In both cases, the conversion was limited to a low level to ensure a high degree of chain end functionality. Then the coupling reaction between the azide end group in $pMA-N_3$ and alkyn-functionalized PgBiB-pSt was performed by Cu(I)catalysis. This coupling reaction was monitored by gel permeation chromatography (GPC). The synthesized block copolymer was characterized by FT-IR, $^1H-NMR$ spectroscopy and $^1H-^1H$ COSY correlation spectroscopy.

• Bulletin of the Korean Chemical Society
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• v.35 no.3
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• pp.833-838
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• 2014

The energy- and time-dependent branching to the competing dissociation paths are studied by theory for coupled unimolecular dissociations of the o-, m-, and p-chlorotoluene radical cations to $C_7{H_7}^+$ (benzylium and tropylium). There are four different paths to $C_7{H_7}^+$, three to the benzylium ion and one to the tropylium ion, and all of them are coupled together. The branching to the multiple paths leads to the multiexponential decay of reactant with the branching ratio depending on both internal energy and time. To gain insights into the multipath branching, we study the detailed kinetics as a function of time and internal energy on the basis of ab inito/RRKM calculations. The number of reaction steps to $C_7{H_7}^+$ is counted for each path. Of the three isomers, the meta mostly goes through the coupling, whereas the para proceeds with little or no coupling. In the beginning, some reactants with high internal energy decay fast to the benzylium ion without any coupling and others rearrange to the other isomers. Later on all three isomers dissociate to the products via long-lived intermediates. Thus, the reactant shows a multiexponential decay and the branching ratio varies with time as the average internal energy decreases with time. The reciprocal of the effective lifetime is taken as the rate constant. The resulting rate-energy curves are in line with experiments. The present results suggest that the coupling between the stable isomers is thermodynamically controlled, whereas the branching to the product is kinetically controlled.

• Journal of the Korean Chemical Society
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• v.12 no.3
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• pp.128-137
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• 1968

In the oligomerization of p-aminophenol by the catalytic action of Fe-EDTA complex in the aqueous medium, the mixed complex intermediate, Fe-EDTA-M type, is considered to be formed, from which active radicals of the monomer are produced. In this system, polymerization is presumed to proceed as follows: Free radical formation ${\to}$ Coupling ${\to}$ Activation ${\to}$ Coupling, and so on. In this study, the form of the monomer and coordination state in the mixed complex, the catalytic action of Fe-EDTA the complex, the reaction mechanism, and the structure of the oligomers are discussed.

• Macromolecular Research
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• v.13 no.3
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• pp.229-235
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• 2005

Various alkoxyamine initiators for nitroxide mediated radical polymerization (NMRP) were prepared in high yields by a simple substitution reaction of nitroxide anions with benzyl bromide. The required nitroxide anions were easily generated by treating either nitroxide free radicals or hydroxy amine with an alkali metal such as sodium or potassium in THF. This method is both practical and efficient, since the ionic conditions prevent other side reactions from occurring, such as the self-coupling or oligomerization reactions that are observed in the case of radical trapping conditions. To demonstrate the utility of the resulting alkoxyamine initiators, end- and telechelic-alkoxyamine PEG macroinitiators derived from the alkoxyamines were synthesized by a simple chemical modification, and used for the preparation of PEG-b-PS and PS-b-PEG-b-PS block copolymers by NMRP.

• Applied Biological Chemistry
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• v.42 no.4
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• pp.330-335
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• 1999

Pentachlorophenol(PCP), which is very persistent in soil and water environment, was tried to detoxify with oxidoreductive catalysts(peroxidase, laccase, tyrosinase and birnessite). To find out detoxification of PCP, the transformation of PCP through oxidative coupling was investigated in the presence of various oxidoreductive catalysts. PCP incubated with peroxidase was significantly transformed, however, in case of tyrosinase, the transformation was negligible. Using peroxidase, the optimal reaction condition was pH 5.6 and $16^{\circ}C$. The transformation of PCP was very fast in initiation step until 30 min but, that was not observed after 180 min. The transformation of PCP was increased by increasing peroacidase amount. When the effect of humic monomer was investigated as co-substrate on the transformation of PCP, the transformation of PCP was mostly decreased in the incubation with peroxidase, laccase, and birnessite. The transformation of PCP, however, was slightly increased by the incubation with tyrosinase in the presence of humic monomers as co-substrate, except catechol. On the basis of the results obtained, it may be suggested that PCP is able to be effectively detoxified through oxidative coupling mediated with oxidoreductive catalysts.

• Polymer(Korea)
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• v.33 no.2
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• pp.158-163
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• 2009

In this study, we synthesized a series of dendritic polystyrene-b-linear poly (t-butyl acrylate) copolymers with well-defined molecular architectures. The hydroxyl group located at the focal point of the second generation dendron bearing polystyrene ($M_n$ = 1000 g/mol) peripheries was converted into amine group via the following stepwise reactions: 1) tosylatoin, 2) azidation, and 3) reduction. On the other hand, the linear poly (t-butyl acrylate)s were prepared by an atom transfer radical polymerization (ATRP) of t-butyl acrylate where benzyl 2-bromopropanoate and Cu(I)Br/PMDETA were used as initiator and catalyst, respectively. To convert the end group of prepared poly (t-butyl acrylate) s into carboxylic acid, a debenzylation was performed using Pd/C catalyst under $H_2$ atmosphere. In the final step, dendritic-linear block copolymers were obtained through a simple amide coupling reaction mediated by 4-(dimethylamino) pyridine(DMAP) and N,N'-diisopropylcarbodiimide(DIPC). The resulting diblock copolymers were shown to have well-defined molecular weights and narrow molecular weight distributions as supported by $^1H$-NMR spectroscopy and gel permeation chromatography(GPC).

• Journal of Korean Society for Atmospheric Environment
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• v.18 no.E2
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• pp.107-120
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• 2002

Dimethyl sulfide (DMS) is the major sulfur gas released from the ocean. The atmospheric DMS released from the ocean is oxidized mainly by hydroxyl (OH) radical during the day and nitrate (NO$_3$) radical at night to form sulfur dioxide (SO$_2$) as well as other stable products. The oxidation mechanism of DMS via OH has been known to proceed by two channels; abstraction and addition channels. The major intermediate product of the addition channel has been known to be dimethylsulfoxide (DMSO) based on laboratory chamber studies and field experiments. However, a branching ratio for DMSO formation is still uncertain. The reaction of DMSO with OH ultimately produces SO$_2$and dimethylsulfone. The major product of the abstraction channel has known to be SO$_2$from laboratory chamber studies. But overall conversion efficiency for DMS to SO$_2$from DMS oxidation is still inconsistent in the literature. Based on laboratory and field studies, the conversion efficiency from the abstraction channel is likely to be greater than 0.5, while that from the addition channel is likely to be greater than 0.6. Overall conversion efficiency from DMS to SO$_2$might be greater than 0.5 based on the above two values in the remote marine boundary layer (MBL). This high efficiency in the remote MBL is supported by strong coupling between DMS and SO$_2$measurements with high temporal resolution.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.11 no.2
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• pp.95-100
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• 1998

A helical inductively coupled plasma asher, which produces low energy and high density plasma, has been built and investigated for photoresist stripping process. Oxygen ion density in the order of $10^{11}/cm^3$ is measured by Langmuir probe, and higher oxygen radical density is observed by Optical Emission Spectrometer. As RF source power is increased, the plasma density and thus photoresist stripping rate are increased. Independent RF bias power to the wafer stage provides a dc bias to the wafer and an ability to add the ion assisted reaction. At 1 KW of the source power, the coupling mechanism of the RF power to the plasma is changed from the inductive mode to the capacitive one at about 1 Torr. This change causes the plasma density and ashing rate decreases abruptly. The critical pressure of the mode change becomes larger with larger RF power.