• 대한화학회지
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• 제31권2호
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• pp.133-142
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• 1987

시클로로펜타디엔과 메틸기로 치환된 알렌의 산 및 에스테르간의 (4+2)고리화반응에서 입체 선택성을 $\pi$-비결합상호작용($\pi$-NBI)을 적용하여 고찰하였다. 열반응에서는 diene(LUMO)-dienophile (HOMO)만을 고려한 2-FMO방법이, 산촉매반응에서는 diene (HOMO)-dienophile (LUMO)상호작용만을 고려한 2-FMO방법이 이들의 입체선택성의 결정에 중요하였다. cumulated diene계의 친디엔체에서 메틸 치환기는 알렌구조와 through-bond 상호작용에 의해 $\pi$-isoconjugate diene 구조를 형성하여 컨쥬게이션기로 작용하며 FMO의 에너지에 narrowing effect를 주고 있으나 이같은 $\pi$-isoconjugated diene 구조를 만들 수 없는 친디엔체에서는 메틸기가 단순히 전자주는기로 작용한다. 열반응에서 입체선택성은 에틸렌 분자와 마찬가지로 메틸 치환기의 $\pi$-비결합 2차궤도 상호작용($\pi$-NSOI)에 의해서 좌우되었다.

• 한국식품과학회지
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• 제28권3호
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• pp.440-445
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• 1996

Methyl linoleate를 기질로하여 온도 및 과산화물가에 따른 monohydroperoxide 이성체의 조성변화를 $60^{\circ}C$와 $90^{\circ}C$ 그리고 $120^{\circ}C$와 $150^{\circ}C$에서 조사하여 보았다. Silica gel column으로 분획한 monohydroperoxide 분획물을 NaBH로 환원시켜 HPLC를 이용하여 분석 및 분획하였다. 각각의 이성체 분획은 trimethylsolyl ester 형태로 유도체화시킨 후 GC-MS로 확인하였다. 확인된 이성체중 기하이성체의 조성변화는 $60^{\circ}C$와 $90^{\circ}C$의 경우 9/13-OOH-trans, trans-diene이 9/13-OOH-cis, trans-diene보다 높게 나타났으나 $150^{\circ}C$의 초기단계에서는 9/13-OOH-cis, trans-diene이 9/13-OOH-trans, trans-diene 보다 다소 높게 나타났다. 한편 위치이성체의 경우에는 온도 및 과산화물가의 변화에 따라 거의 비슷한 비율을 나타내었다.

• 대한화학회지
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• 제26권1호
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• pp.7-17
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• 1982

Diels-Alder 반응의 배향성에 대한 치환기 및 산촉매 효과를 예측하기 위해 또 Lewis산이 diene, dienophile과의 착물 형성의 경쟁성을 예측하기 위해서 Diels-Alder 반응의 열 또는 촉매반응에 FMO이론을 적용하여 CNDO/2 방법으로 고찰하였다. (1)Acetoxy로 치환된 diene의 카르보닐 산소는 dienophile보다 더 큰 음 전하를 갖기 때문에 Lewis 산이 dienophile보다는 diene에 우선적으로 배위하였다. (2) 본 연구의 대부분의 반응은 Neutral electron demand 반응형태를 가지므로 4-c, 2-c 및 정량적인 SOI방법이 일반적으로 실험적인 주 배향체와 일치함을 알았다. (3) 황은 빈 d-궤도 함수의 참여로 인해서 산소에 비해 치환기의 인접된 말단 탄소원자의 LUMO를 크게 활성화 시켜 Neutral electron demand 반응에서의 diene LUMO-dienophile HOMO 상호작용을 크게 해주어 배향성 결정에 주도적 역할을 하게 되었다.

• 대한화학회지
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• 제31권4호
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• pp.334-343
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• 1987

$NiL_m{^{2+}}$착이온 {$Ni(rac-1[14]7-diene)^{2+},\;Ni(meso-1[14]7-diene)^{2+},\;Ni(1[14]4-diene)^{2+},\;{\alpha}-Ni(rac-[14]-decane)^{2+},\;{\beta}-Ni(rac-[14]-decane)^{2+},\;and\;Ni(meso-[14]-decane)^{2+}$}과 $CN^-$이온 사이의 화학반응은 분광광도법으로 연구하였다. $NiL_m{^{2+}}$착이온과 $CN^-$이온으로부터 1:1착이온, $[NiLm(CN)]^+$생성반응의 평형상수$(K_1)$는 3 ~ $25^{\circ}C$ 범위에서 결정되었다. $NiL_m{^{2+}}$착이온이 $Ni(rac-1[14]7-diene)^{2+},\;Ni(meso-1[14]7-diene)^{2+},\;Ni(1[14]4-diene)^{2+},\;{\alpha}-Ni(rac-[14]-decane)^{2+},\;{\beta}-Ni(rac-[14]-decane)^{2+}$, 그리고 $Ni(meso-[14]-decane)^{2+}$일때 평형상수($K_1$)은 $15^{\circ}C$에서 각각 4.7, 5.3, 6.2, 7.5, 9.4, 및 9.8이었다. $K_1$값은 온도가 증가함에 따라 감소하였다. $K_1$에 대한 온도영향으로 부터 열역학적 파라메터 $({\Delta}G^{\circ},\;{\Delta}H^{\circ},\;{\Delta}S^{\circ})$를 계산하였으며, 이 결과 $[NiLm(CN)]^+$ 생성반응은 모두 발열반응으로 나타났다. $NiL_m{^{2+}}$ 착이온과 $CN^-$이온은 반응하여 Ni(CN)_4{^{2-}}$이온과 거대고리 리간드 (Lm)가 생성된다. $[CN^-],\;[HCN],\;and\;[OH^-]$ 변화에 따라 $Ni(CN)_4{^{2-}}$이온의 생성속도는 0.5M $NaClO_4$, 온도 3∼$25^{\circ}C$ 범위에서 연구되었다. $[CN^-]$가 일정할 때 [HCN]가 증가하면 $k_{obs}/[CN^-]^2$값은 선형으로 증가하였다. $OH^-$ 이온이 과량으로 존재할 때 [$OH^-$]에 따라 역시 $k_{obs}/[CN^-]^2$ 값은 선형으로 증가하였다. $NiL_m{^{2+}}$ 착이온과 $CN^-$이온 반응의 속도상수($k_{obs}$)에 대한 온도영향으로 부터 활성화 파라메터$({\Delta}H^{\neq},\;{\Delta}S^{\neq})$를 결정하였다. $Ni(rac-1[14]7-diene)^{2+},\;Ni(meso-1[14]7-diene)^{2+},\;{\alpha}-Ni(rac-[14]-decane)^{2+},\;{\beta}-Ni(rac-[14]-decane)^{2+}$, 그리고 $Ni(meso-[14]-decane)^{2+}$ 순서로 d-d 전이에너지, $ν(cm^{-1})$가 감소할수록, ${\Delta}H^{\neq}$도 점차적으로 감소하였다. 그리고 5가지의 $NiL_m{^{2+}}$ 착이온과 $CN^-$이온 사이의 반응은 동일한 경로로 반응이 진행되었다.

• Journal of Pharmaceutical Investigation
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• 제40권3호
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• pp.155-160
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• 2010

A gas chromatographic-mass spectrometric (GC-MS) method was developed for the simultaneous determination of valproic acid (VPA) and its toxic metabolites, 4-ene-VPA and 2,4-diene-VPA in rat plasma. Extraction was performed in weak acidic condition (pH 5.2) to avoid degradation of 4-ene-VPA and 2,4-diene-VPA. The recoveries for 4-ene-VPA and 2,4-diene-VPA were more than 70% and that for VPA was 33-42%. R value for each compounds exceeded 0.998 in calibration curve during all the analysis. Accuracy and precision ranged from 88.3 to 113.2% and from 2.16 to 14.2%, respectively The method was successfully applied to monitor plasma concentrations of VPA, 4-ene-VPA and 2,4-diene-VPA after intravenous administration of VPA at the dose of 100 mg/kg, suggesting that these toxic metabolites may involved in the hepatotoxicity induced by VPA.

• Elastomers and Composites
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• 제7권1호
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• pp.21-37
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• 1972

We have studied the blending effects of Diene NF 35R and Turfdene 1000R at various blending ratios 100/0, 70/30, 50/50, 30/70, 0/100, and of carbon black NAF and ISAF at various compounding ratios of 55 PHR, 65PHR, 75PHR for tyre tread rubber. As the results, it was found that; 1. For tyre tread rubber, as the blending ratio, Diene NF 35R/Turfdene 1000R, indicated 30/70, the physical properties we examined were most excellent. 2. Excellent result was obtained in case of carbon black compounding ratio of 63PHR. The compounding of ISAF made better result than that of HAF for tensile strength, tearing strength, and abrasion quantity. 3. Heat buildup obtained from compounding carbon black HAF indicated low temperature than that from compounding carbon black ISAF. As the compounding amount of carbon black increased, the heat buildup improved, and as the blending amount of Diene NF 35R decreased, the heat buildup dropped. 4. Carbon black was more efficient to Turfdene 1000R than to Diene NF 35R. 5. In this pysical properties, mooney viscosity, and mooney scorch time, as the compounding amount of carbon black increased, the values of mooney viscosity increased, but that of mooney scorch time dropped.

• Elastomers and Composites
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• 제6권2호
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• pp.47-63
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• 1971

We have studied the blending effects of Diene 33R and styrenebutadiene rubber at various blending ratios of 100/0, 70/30, 50/50, 30/70, 0/100, and of carbon black HAF and ISAF at various compounding ratios of 55 PHR, 65 PHR, 75 PHR for tyre tread rubber. As the results, it was found that ; 1. For tyre tread rubber, when the blending ratio, Diene NF 35R/SBR 1778, indicated 30/70, the physical properties we examined were most excellent. 2. Excellent result was obtained in case of carbon black compounding ratio of 65 PHR. The compounding of ISAF made better result than that of HAF for abrasion quantity, tearing strength, and tensile strength. 3. Heat buildup obtained from compounding carbon black HAF indicated low temperature than that from compounding carbon black ISAF. As the compounding amount of carbon black increased, the heat buildup improved. And as the blending amount of Diene NF 35R decreased, the heat buildup dropped. 4. Carbon black was more efficient to SBR than to Diene Rubber. 5. It is a shortage that elongation revealed low price.

• Elastomers and Composites
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• 제23권4호
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• pp.308-323
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• 1988

• 한국식품영양학회지
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• 제28권1호
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• pp.40-46
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• 2015

Hamcho (Salicornia herbacea) extracts were evaluated for total polyphenol content, antioxidant and pro-oxidant activities. The total polyphenol content was 1.81 g and 0.72 g per 100 g of dried sample in water and ethanol extracts respectively. Both water and ethanol extracts of Hamcho significantly exhibited antioxidant activity. The scavenging activity of hydroxyl radical was 13.8~26.2% and 14.2~16.0% in water and ethanol extracts respectively. The inhibitory effect of conjugated diene formation was 24.6~39.1% and 28.4~39.6% in water and ethanol extracts respectively. However, pro-oxidative effect was also observed in the Hamcho extracts. The Hamcho water extract showed the pro-oxidant effect by enhancing the formation of hydroxyl radical and conjugated diene. The ethanol extract of Hamcho induced conjugated diene formation at 0.5 mg/mL but not at 1 mg/mL. The hydroxyl radical formation was not induced by the Hamcho ethanol extract. Taken together, these results show that Hamcho extracts can act as pro-oxidants by generating hydroxyl radical or conjugated diene in addition to their antioxidant properties. Therefore, this study suggests that the physiological properties of Hamcho and its use as food materials should be considered with caution because antioxidant dietary plants such as Hamcho possess possible adverse effects induced by pro-oxidant activity.

• 생약학회지
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• 제19권4호
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• pp.228-232
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• 1988

From the rhizome of Atractylodes japonica Koidzumi (Compositae) which is the original plant of oriental medicine 'Cang-Zhu', four essential oil compounds were isolated. Three of them were identified as atractylon, hydroxyatractylon and $5{\alpha}H,\;10{\beta}-selina-4(14),\;7(11)-diene-8-one$, which were already known as the constitutents of Atractylodes Rhizoma. The fourth is a novel polyacetylene type compound, and the structure is postulated as 1, 4-diacetoxytetradeca-6, 12-diene-8, 10-diyne by the spectral data.