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Synthesis and Properties of Nonlinear Optical Polymer Derived from α-Methyl Styrene/Maleic Anhydride by Polymer Reaction (고분자 반응을 이용한 Maleic anhydride계 비선형 광학 고분자의 합성 및 전기광학 특성)

  • Park, Lee Soon;Keum, Chang Dae;Song, Jae Won;Kim, Kwang Taek;Kim, Gi Heon;Kang, Shin Won
    • Applied Chemistry for Engineering
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    • v.9 no.5
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    • pp.704-709
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    • 1998
  • Non-linear optical polymer based on poly (${\alpha}$-methylstyrene-co-maleic anhydride) (MSMA) substrate polymer was prepared by polymer reaction method and its thermal and electro-optic properties were examined. In the polymer reaction between MSMA substrate polymer and 2-[4-(4-nitrophenylazo)-N-ethylphenylamino]ethanol (DR1) chromophore, the degree of substitution of DR1 into MSMA was higher with the 4-dimethylaminopyridine (DMAP) as catalyst and 3-dicyclohexyl carbodiimide (DCC) as dehydrating agent (sample, MSMA-DC) than the one with just 4-dimethylaminopyridine as catalyst (sample, MSMA-D). The synthesized NLO polymer (MSMA-DC) exhibited electro-optic coefficient of 18 pm/V (632.8 nm) and glass transition temperature ($T_g$) of about $175^{\circ}C$.

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Metal-Dinitrosyl Complexes(Ⅳ) : Synthesis and Characterization of Symmetric and Asymmetric Dinuclear Molybdenum and Tungsten Complexes (금속-디니트로실 착물 (제 4 보) : 몰리브덴과 텅스텐의 대칭 및 비대칭 이핵 착물의 합성과 특성)

  • O, Sang O;Mo, Seong Jong
    • Journal of the Korean Chemical Society
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    • v.38 no.7
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    • pp.485-495
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    • 1994
  • Several new symmetric and asymmetric homo and hetero dinuclear complexes of the type $[Cl(dppp)(NO)_2M({\mu}-pyz)M'(NO)_2(dppp)Cl][ClO_4]_2$ and $[Cl(phen)(NO)_2M({\mu}-pyz)M'(NO)_2(dppp)Cl][ClO_4]_2$(M,M'= Mo or W; phen = 1,10-phenanthroline; dppp = 1,3-bis(diphenylphosphino)propane; pyz = 1,4-pyrazine) were synthesized in three-steps starting from $[M(NO)_2Cl_2]_n(M = Mo, W)$. The final products were purified by eluting it through silica gel column ($2{\times}20$ cm) with acetone as the eluent. Characterization of these complexes and some related complexes was accomplished through UV-vis., $^1H$-NMR, $^{13}C$-NMR and IR spectroscopies as well as elemental analysis. The infrared spectra indicate that the NO groups occupy cis-positions of the octahedral. The $^1H$ and $^{13}C-NMR$ data for the new compounds revealed a dimeric structures with bridged pyz.

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Kinetics of the Reaction of Phenacyl Bromide with Anilines in Methanol and Dimethylformamide (Phenacyl Bromide와 置換아닐린類와의 反應에 關한 反應速度論的 硏究)

  • Soo-Dong Yoh;Doo-Jung Kim
    • Journal of the Korean Chemical Society
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    • v.25 no.6
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    • pp.376-382
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    • 1981
  • The rates and the activation parameters for the reaction of phenacyl bromide with substituted anilines in methanol and dimethylformamide were measured. The effects of substituted anilines were discussed. The rate of the reaction was increased with the electron donating power of substituent and showed larger value in DMF than in MeOH. The isokinetic relationship was shown between ${\delta}H^{\neq}$ and ${\delta}S^{\neq}$, isokinetic temperature was 539 and $400^{\circ}C$ in MeOH and DMF respectively, but p-nitro aniline was deviated from linearity in both solvents caused by solvent effects. The excellent linear relationship between log k and p$K_a$ of substituted anilines was observed by following equation. log k = 0.57p$K_a$-1.28 (r = 0.996) in MeOH at $45^{\circ}C$, log k = 0.65p$K_a$-0.88 (r = 0.970) in DMF at $45^{\circ}C$. From the Hammett plot, this reaction was a nucleophilic displacement of aniline to phenacyl bromide and the following equation was obtained at $45^{\circ}C$. log k/$k_0$ = -2.00${\sigma}$ + 0.06 (r = 0.985) in MeOH; log k/$k_0$ = -2.22${\sigma}$ + 0.08 (r = 0.995) in DMF. Large deviation of p-nitro aniline in DMF is resulted from solvent effects too. From above results, the substituent effect of this reaction can be described as $S_N2$ mechanism and bond formation more proceeds in DMF relative to MeOH.

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Kinetics and Mechanism of the Hydrolysis of N-(p-Nitrophenyl)-benzohydrazonyl Azide Derivatives (N-(p-니트로페닐)-벤조히드라조닐아지드 유도체의 가수분해 반응메카니즘과 그의 반응속도론적 연구)

  • Nack-Do Sung;Ki-Sung Kwon;Tae-Rin Kim
    • Journal of the Korean Chemical Society
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    • v.22 no.3
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    • pp.150-157
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    • 1978
  • The rate constants for the hydrolysis of the derivatives of N-(p-nitrophenyl)-benzohydrazonyl azide (p-$CH_3,\;p-CH_3O,\;p-NO_2$, p-Cl, p-Br) have been determined by UV spectrophotometry in 50% dioxane-water at $25^{\cicr}C$ and a rate equation which can be applied over wide pH range was obtained. Below pH 5, the rate of hydrolysis of hydrazonyl azides is accelerated by electron-donating group ($\rho$ = -0.47), whereas at the pH values greater than 7, the $\rho$-value is 0.68. The effect of salt, solvent, substituent and azide ion on the rate of hydrolysis are rationalized in terms of $S_N1$ and $S_N2$ mechanism; below pH 5, the hydrolysis proceed through $S_N1$, however, above pH 7, the hydrolysis is started by the attack of hydroxide ion and in the range of pH 5∼7, these two reactions occur competitively.

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Degradation of Quercus serrata by Lentinus edodes (Berk) Singer (골목성분(?木成分)의 분해(分解))

  • Yoon, Byung-Ho
    • Journal of the Korean Wood Science and Technology
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    • v.6 no.1
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    • pp.3-7
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    • 1978
  • Quercus serrata degraded by Leminus edodes(berk) Singer was investigated. In order to evaluate on affect of the fungi on the sound logs, and the logs attacted for 2 years and five years were used as a sample tree. Large portions of carbohydrate mainly was decomposed by the fungy. It is supported by the increasing of alkaline extractives and the breaking up of crystallinity. Lignin is transformed considerably as shown the results of the determination of Klason lignin, gel filtration and nitrobezene oxidation. On the other hand, the decreasing of methoxyl group and the increasing of carboxyl group in parallel with demethlation and acidification are presented. Syringyl nuclei unit is decomposed easier than guaiacyl unit. It is also illustrated that the more decreasing of carboxyl group compared with aldehyde group was acidified biodegradation.

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Synthesis of High Purity p-Phenylenediamine from p-Nitroaniline by Catalytic Hydrogenation (Pd/C촉매하 파라니트로아닐린 수소첨가에 의한 고순도 파라페닐렌디아민의 합성공정)

  • Cho, Chul Kun;Chung, Kwang Bo
    • Applied Chemistry for Engineering
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    • v.10 no.8
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    • pp.1210-1215
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    • 1999
  • Optimum conditions of the hydrogenation of PNA to pure PPD were determined in a three-phase slurry reactor with suspended Pd/C catalyst particles. Minimization of mass transfer resistances at the interfaces of both gas-liquid and liquid-catalyst particles and control of overall reaction rate on catalyst surface leaded to decrease the hydrogen starvation on reaction active sites and to reduce the side reactions during hydrogenation. The optimum temperature, pressure, and catalysst concentration were confirmed to be in the range of $60^{\circ}C$, 60~70 psig, and 1~2 g-cat/L, respectively. Reaction rate was zero order with respect to the concentration of PNA and 1st order with respect to the pressure of hydrogen(P). Overall rate expression of the reaction was $R_A=6.44{\times}10^6{\cdot}H{\cdot}P{\cdot}m{\cdot}$exp(-4659/T) where H is constant, m is concentration of catalyst, and T is temperature.

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Reductive degradation of Chlorinated compounds by using Iron Minerals (철 광물에 의한 염소계 유기화합물의 환원적분해)

  • Kim, Sung-Kuk;Park, Sang-Won
    • Journal of Soil and Groundwater Environment
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    • v.9 no.2
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    • pp.11-19
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    • 2004
  • Chlorinated and nitroaromatic compounds are non-degradable substances that are extremely toxic and are known to be carcinogens and mutation causing agents. Moreover, the half-lives of substances such as carbon tetrachloride, hexachloroethane and nitroaromatic compounds are several decades. In this study, the optimal conditions to detoxify chlorinated compounds by the reductive degradation were investigated. The following results were obtained in the reductive degradation of CCl$_4$, C$_2$Cl$\_$6/, C$_2$HCl$\_$5/, C$_2$Cl$_4$, and C$_2$HCl$\_$5/ by using Fe, FeS and FeS$_2$ as mediators. CCl$_4$ was reduced to CH$_2$Cl$_3$ and CH$_2$Cl$_2$in anaerobic conditions when FeS was used as a mediator. While the reduction of CCl$_4$ to CHCl$_3$ was rapidly proceeded, the reduction of CHCl$_3$ to CH$_2$Cl$_2$ was occurred slowly. Further reduction to CH$_3$Cl was not observed. Unlike CCl$_4$, C$_2$Cl$\_$6/ was degraded to C$_2$HCl$\_$5/, C$_2$Cl$_4$. C$_2$HCl$_3$ and cis-1,2-C$_2$H$_2$Cl$_2$ by complicated pathways such as hydrogenolysis, dehalo-elimination and dehydrohalogenation. A small amount of C$_2$HCl$\_$5/ was detected only in the early stages of the reduction. However, majority of the C$_2$Cl$\_$6/ was reduced to C$_2$Cl$_4$. cis-1,2-C$_2$H$_2$C1$_2$ was the only product among other possible isomers.

Degradation of the Selected Pesticides by Gas Discharge Plasma (기체플라즈마에 의한 농약분해특성 연구)

  • Min, Zaw Win;Hong, Su-Myeong;Mok, Chul-Kyoon;Im, Geon-Jae
    • The Korean Journal of Pesticide Science
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    • v.16 no.1
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    • pp.11-20
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    • 2012
  • As increasing the use of pesticides both in number and amount to boost crop production, consumer concerns over food quality and safety with respect to residual pesticides are also continuously increasing. However, there is still lacking of information that can effectively help to remove residual pesticides in foods. In recent years, contaminant removal by gas (or) glow discharge plasma (GDP) attracts great interests on environmental scientists because of its high removal efficiency and environmental compatibility. It was shown to be effective for the removal of some organophosphorus pesticides, phenols, benzoic acid, dyes, and nitrobenzene on solid substrate or in aqueous solution. This work mainly focuses on the removal of wide range of residual pesticides from fresh fruits and vegetables. As for preliminary study, the experiments were carried out to investigate whether GDP can be used as an effective tool for degrading target pesticides or not. With this objective, 60 selected pesticides drop wised onto glass slides were exposed to two types of GDP, dielectric barrier discharge plasma (DBDP) and low pressure discharge plasma (LPDP), for 5 min. Then, they were washed with 2 mL MeCN which were collected and used for determination of remaining concentration of pesticides using LC-MS/MS. Among selected pesticides, degradation of 18 pesticides (endosulfan-total was counted as one pesticide) by GDP could not be examined because control treatments, which were left in ambient environment, of those pesticides recovered less than 70% or even did not recover. However, majority of tested pesticides (42) were degraded by both types of GDP with satisfactory recovery (>80%) of control sample. Pesticides degradation ranged from 66.88% to 100% were achieved by both types of plasma except clothianidin which degradation in LPDP was 26.9%. The results clearly indicate that both types of gas discharge plasma are promising tools for degrading wide range of pesticides on glass substrate.

Photochromic Spiropyran-Functionalized Organic-Inorganic Hybrid Mesoporous Silica for Optochemical Gas Sensing (광화학적 가스 센싱을 위한 광변색 스피로피란 개질된 유기-무기 하이브리드 메조포러스 실리카)

  • Park, Sung Soo;Ha, Chang-Sik
    • Journal of Adhesion and Interface
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    • v.17 no.4
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    • pp.141-148
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    • 2016
  • In this work, mesoporous silica (SBA-15) was synthesized via self-assembly process using triblock copolymer ($PEO_{20}PPO_{70}PEO_{20}$, P123) as template and tetraethyl orthosilicate (TEOS) as silica source under acidic condition. SBA-15 have high surface area ($704m^2g^{-1}$) and uniform pore size (8.4 nm) with well-ordered hexagonal mesostructure. Spiropyran-functionalized SBA-15 (Spiropyran-SBA-15) was synthesized via post-synthesis process using 3-(triethoxysilyl)propyl isocyanate (TESPI) and 1-(2-Hydroxyethyl)-3,3-dimethy-lindolino-6'-nitrobenzopyrylo-spiran (HDINS). Spiropyran-SBA-15 was produced with hexagonal array of mesopores without damage of mesostructre. Surface area and pore size of Spiropyran-SBA-15 were $651m^2g^{-1}$ and 8.0 nm, respectively. Optochemical properties of Spiropyran-SBA-15 was studied with chemical vapors such as EtOH, THF, $CHCl_3$, Acetone and HCl. Main peaks of photofluorescence of Spiropyran-SBA-15 exhibited blue shift in the range of 603.4~592.1 nm after exposure under EtOH, THF, $CHCl_3$, and Acetone vapors. Normalized peak intensities decreased in the range of 0.8~0.3. The main peak of photofluorescence of Spiropyran-SBA-15 showed significant blue shift of 592.1 nm after exposure under HCl vapor, while normalized peak intensity decreased to 0.1.

Ecology and Chemical Control of Caliroa carinata (Hymenoptera : Tenthredinidae) (남포잎벌의 생태(生太)와 방제(防除)에 관(關)한 연구(硏究))

  • Kim, Chul-Su;Park, Ji-Doo;Park, Young-Seuk;Lee, Sang-Gil;Shin, Sang-Chul
    • Journal of Korean Society of Forest Science
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    • v.89 no.5
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    • pp.685-690
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    • 2000
  • Caliroa carinata (Zombori) has heavily damaged the forests of Quercus mongolica in Sangju, Kyongbuk, Korea since 1996. However, information on the ecology and control of this pest was badly scarce. Thus we tried to study the ecology and chemical control of the sawfly through this study. Caliroa carinata is one generation per year. The adult sawflies emerged from June 8 to July 5 with peak at June 18. A female adult laid 11 eggs in rows on the backside of a leaf along the midribs and larger veins. Larvae have six instars, and the developmental period required to complete the larval stage was 19 days and 17 days at temperatures of $20^{\circ}C$ and $25^{\circ}C$, respectively. Each larval stage required 2-4 days to complete the development. The sawfly mostly preferred Quercus mongolica and Q. dentata, while avoiding Q. variabilis. Such insecticides as Tebufenozide, Flufenoxuron, Etofenprox, and Fenitrothion were sprayed on host plant leaves infected with test larvae in order to study the mortality. After 3 days of insecticide treatments, the mortalities were thoroughly examined. All insecticides showed higher than 95% of mortalities. Control values were also higher than 93%. The optimal season of insecticide application for pest control was estimated from late June to early July.

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