• Title/Summary/Keyword: carbonyl group

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Theoretical Studies on the Reactions of Acetate Esters with Substituted Phenolate Anion Nucleophiles$^1$

  • Im, Ung Muk;Kim, Wang Gi;Jeong, Hak Jin;Lee, Ik Jun
    • Bulletin of the Korean Chemical Society
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    • v.16 no.3
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    • pp.252-256
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    • 1995
  • Semiempirical MO calculations using the PM3 method are performed on the reactions of acetate esters with substituted phenolate anions. The mechanistic change from rate-limiting formation to breakdown of the anionic intermediate is shown to occur in the gas-phase, especially for meta-nitrophenyl acetate. However the mechanistic change-over takes place at a lower basicity ($pK_0$) of the anion nucleophile than found for the corresponding formate. This lowering of $pK_0$ has been ascribed to the electron donating effect of the methyl group in the acetate. For the reactions involving rate-limiting breakdown of the intermediate, the large Bronsted coefficients, ${\beta}_X({\beta}_{nuc})$, are expected in general, but the magnitude increases to a larger value and the pK0 is lowered accordingly, when an electron-donating nonleaving group, like $CH_3$, is present. This type of nonleaving group effect provides a necessary condition for the carbonyl addition-elimination mechanism with rate-limiting breakdown of the intermediate.

Increasing Effect on Storage Stability of Rosemary Extracts used for Various Solvent System on Seasoning Oils (향미유 제품에 대한 추출 용매별 로즈마리 추출물의 저장 안정성 향상 효과)

  • Lee, Jang-Woo;Ahn, Young-Soon;Hong, Young-Pyo;Han, Myung-Kyu
    • The Korean Journal of Food And Nutrition
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    • v.19 no.3
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    • pp.271-278
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    • 2006
  • As for red pepper seasoning oil (RPSO), seasoning oil (SO) and pine needle oil (PNO), various organic solvent extracts from rosemary powder and tocopherol are treated as control group. At this time, amounts that are treated were all 1,000 ppm. It was observed by AV (acid value), POV (peroxide value) and carbonyl compounds content of the stored samples during 3 months at 60${\pm}$2$^{\circ}C$ incubation. Tocopherol was shown to be pro-oxidant than the antioxidant in all seasoning oil samples. Icreasing effect of storage stability of chloroform/MeOH extract was the most superior one. Final result of icreasing effect of storage stability from the determinated data was as follows. The storage stability of solvent system by AV and POV analysis was in the increasing order of chloroform/MeOH extract> ethyl alcohol extract>hot water extract>ethyl acetate extract>acetone extract>none treating group> tocopherol treating group, POV was chloroform/MeOH extract>ethyl alcohol extract ${\geq}$ ethyl acetate extract> acetone extract ${\geq}$ hot water extract>none treating group>tocopherol treating group and by carbonyl compound content analysis was in the increasing order of chloroform/MeOH extract>ethyl acetate extract>ethyl alcohol extract>hot water extract>acetone extract>none treating group>tocopherol treating group.

Structural Characteristics of Low Molecular Weight Laminarin Prepared by Ionizing Irradiation (이온화 방사선 조사에 의해 얻어진 저분자 laminarin의 분자구조 특성)

  • Choi, Jong-Il
    • Korean Chemical Engineering Research
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    • v.51 no.6
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    • pp.780-783
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    • 2013
  • Recently, it has been reported that low molecular weight laminarin had the enhanced biological activities. In this study, molecular structure of low molecular weight laminarin prepared by ionizing irradiation was studied. Low molecular weight laminarin samples of 13.5, 8.5, 7, and 6 kDa were obtained from 15 kDa laminarin by irradiation. From gel permeation chromatography data, low molecular weight laminarin was shown to have low polydispersity. To define the changes of functional groups in laminarin with different molecular weights, Fourier-transform infrared analysis was carried out. There was found no significant changes of functional groups in low molecular weight laminarin, except the increase of carbonyl group. The granular fissures from scanning electron microscopy showed the breakage of glycosidic bond in low molecular weight laminarin. These results could be utilized for the investigation of the enhanced biological activities of low molecular weight polysaccharides including laminarin.

Understand the Molecular Orbital Theory on the Hydrolytic Reactivity of Herbicide Flumioxazine (제초제 Flumioxazine의 가수분해 반응성에 관한 분자 궤도론적 이해)

  • Sung, Nack-Do;Jung, Hoon-Sung
    • The Korean Journal of Pesticide Science
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    • v.8 no.4
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    • pp.265-271
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    • 2004
  • Hydrolytic reactivities of N-phenylphthalimid herbicide flumioxazine (S) were disccused using molecular orbital (MO) theoretical method. It is revealed that below pH 5.0, the protonation $(SH^+)$ to carbonyl oxygens atom $(O_{21})$ of 1,2-dicarboximino group by general acid catalysis $(k_A)$ with hydronium ion $(H_3O^+)$ proceeds via charge controled reaction. Whereas, the specific base catalysis $(k_{OH})$ with hydroxide anion via orbital controled reaction occurs above pH 8.0. We may concluded that in the range of pH $5.0\sim8.0$, the hydrolysis proceeds through nucleophilic addition elimination $(Ad_{N-E})$ reaction, these two reactions occur competitively.

Effects of cranberry powder on biomarkers of oxidative stress and glucose control in db/db mice

  • Kim, Mi Joung;Chung, Jee-Young;Kim, Jung Hee;Kwak, Ho-Kyung
    • Nutrition Research and Practice
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    • v.7 no.6
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    • pp.430-438
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    • 2013
  • Increased oxidative stress in obese diabetes may have causal effects on diabetic complications, including dyslipidemia. Lipopolysccharides (LPS) along with an atherogenic diet have been found to increase oxidative stress and insulin resistance. Cranberry has been recognized as having beneficial effects on diseases related to oxidative stress. Therefore, we employed obese diabetic animals treated with an atherogenic diet and LPS, with the aim of examining the effects of cranberry powder (CP) on diabetic related metabolic conditions, including lipid profiles, serum insulin and glucose, and biomarkers of oxidative stress. Forty C57BL/KsJ-db/db mice were divided into the following five groups: normal diet + saline, atherogenic diet + saline, atherogenic diet + LPS, atherogenic diet + 5% CP + LPS, and atherogenic diet + 10% CP + LPS. Consumption of an atherogenic diet resulted in elevation of serum total cholesterol and atherogenic index (AI) and reduction of high density lipoprotein (HDL)-cholesterol. However, with 10% CP, the increase in mean HDL-cholesterol level was close to that of the group with a normal diet, whereas AI was maintained at a higher level than that of the group with a normal diet. LPS induced elevated serum insulin level was lowered by greater than 60% with CP (P < 0.05), and mean serum glucose level was reduced by approximately 19% with 5% CP (P > 0.05). Mean activity of liver cytosolic glutathione peroxidase was significantly increased by LPS injection, however it was reduced back to the value without LPS when the diet was fortified with 10% CP (P < 0.05). In groups with CP, a reduction in mean levels of serum protein carbonyl tended to occur in a dose dependent manner. Particularly with 10% CP, a reduction of approximately 89% was observed (P > 0.05). Overall results suggest that fortification of the atherogenic diet with CP may have potential health benefits for obese diabetes with high oxidative stress, by modulation of physical conditions, including some biomarkers of oxidative stress.

Solvent Effects upon Carbonyl Stretching Freguency Shifts of Raman Spectra : Ketones (라만 스펙트럼의 카보닐 신축진동 이동에 대한 용매효과 : 케톤)

  • In Ju Lee;Sung Hun Seo;Mu Sang Lee
    • Journal of the Korean Chemical Society
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    • v.37 no.12
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    • pp.987-994
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    • 1993
  • Inductive and resonance effects play an important role in determining carbony) stretching frequencies of ketones. Hydrogen bonding, dielectric effects, and steric effects are all factors which determine the carbonyl stretching frequency, νC=O of ketones in solution. The $ν_{C=O}$ frequencies were shifted by approximately 27$cm^{-1}$ each by substituting to a phenyl group for a methyl group in acetone. The $ν_{C=O}$ frequency for ketones shifted differently in various solvents and increased with increasing the volume ratio of the ketones in water solutions. The $ν_{C=O}$ frequency for ketones shifts continously at constant concentration of ketone in solutions of $(CH_3)_2SO/CCl_4$and$CHCl_3/CCl_4$ with changing of the mole ratio of two solvents. The $ν_{C=O}$ frequency was also affected by changing concentration in either $CCl_4$ or $(CH_3)_2SO$ solution and in either $CCl_4$or $CHCl_3$ solution.

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Synthesis, Film Fabrication, and Optical Properties of Polymers Containing Metal Cation Complex Type D-$\pi$-A Chromophore (금속 양이온 배위형 D-$\pi$-A 발색단을 포함하는 폴리머의 합성 및 박막화와 광학특성)

  • Jeong, Seon-Ju;Kim, Hye-Ryun;Yoon, Keun-Byoung;Han, Yoon-Soo;Fujiki, Michiya;Takagi, Akiko;Kwak, Gi-Seop
    • Polymer(Korea)
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    • v.34 no.4
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    • pp.376-380
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    • 2010
  • Donor-$\pi$-acceptor (D-$\pi$-A) type chromophore-based polymers were newly synthesized. These polymers exhibited absorption peak due to intramolecular charge transfer (ICT) in a visible range as well as absorption peak due to carbonyl group in both solution and film state by measuring UV visible spectra. The addition of $Eu^{3+}$ ion into the polymers induced red-shift in absorption due to ICT and the color changes from yellow to red in the solution and film were observed by naked eyes. The contents of crosslinking agent influenced the features and solubility of the polymers. In addition, the contents of crosslinking agent and the $Eu^{3+}$ ion addition improved film-forming ability.

Potential of Baeyer-Villiger monooxygenases as an enzyme for polyethylene decomposition (폴리에틸렌 분해를 위한 효소로써 Baeyer-Villiger monooxygenases의 잠재력)

  • Yoon, Ye Rin;Jang, Yu-Sin
    • Journal of Applied Biological Chemistry
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    • v.64 no.4
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    • pp.433-438
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    • 2021
  • Polyethylene is widely used as an agricultural film, but eco-friendly technology is lacking for its decomposition. Thus, recently, much attention has been paid to develop a technology for biological polyethylene decomposition. It has been expected that several oxidation steps will be required in the biological degradation of polyethylene. First, secondary alcohol is formed on the polyethylene chain, and then the alcohol is oxidized to a carbonyl group. In the subsequent process, the carbonyl group is converted to an ester by Baeyer-Villiger monooxygenase (BVMO), and this ester bond is expected to be cleaved by lipase and esterase in the final step. In this work, we reviewed BVMO as one of the promising enzymes for polyethylene decomposition, in terms of its reaction mechanism, classification, and engineering. In addition, we also give a brief perspective on polyethylene decomposition using BVMO.

Pretreatment for Improving Selective Hydrogenation Reaction of α, β-Unsaturated Aldehydes (α, β-불포화 알데히드의 선택적 수소화 반응성 향상을 위한 전처리 방법)

  • Kook-Seung Shin;Mi-Sun Cha;Chang-Soo Lee
    • Korean Chemical Engineering Research
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    • v.61 no.1
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    • pp.168-174
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    • 2023
  • In commercial production processes of methyl methacrylate, there is a methacryl aldehyde as an intermediate or impurities. The existence of impurities is critical factor because of significant decrease of the conversion rate and selectivity of the entire chemical reaction. This study found that an acid was the main cause of the decrease in reactivity among various impurities because an acid rapidly lowers the activity of a catalyst and promotes a side reaction, the hetero Diels-Alder reaction. Therefore, the pretreatment methods with the removal of acid were comparatively evaluated by the selective hydrogenation reaction of the carbonyl group of the reactants. Based on several experimental conditions, we believe that proposed effective pretreatment improves productivity with appropriate economical process.

Photoprotective Effect of Lotus (Nelumbo nucifera Gaertn.) Seed Tea against UVB Irradiation

  • Kim, Su-Yeon;Moon, Gap-Soon
    • Preventive Nutrition and Food Science
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    • v.20 no.3
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    • pp.162-168
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    • 2015
  • Lotus (Nelumbo nucifera Gaertn.) seed is widely used as a traditional medicine in countries of Asia. Among many functions of the lotus seed, one interesting activity is its skin protection from the sunlight and scar. In this study, we focused on the skin protective property of lotus seed tea against ultraviolet B (UVB) irradiation. Two groups of a hairless mouse model, water as control (water group) and lotus seed tea (LST group), were administrated a fluid drink water for six months. After 6 month of administration, UVB exposure was carried out to both groups for another 3 months. During and after the administration, the skin moisture content and the morphological and histopathological analyses through biopsy were carried out. Prior to UVB irradiation, no significant difference was discovered in the skin moisture content for the water group and LST group (P<0.05). However, drastic changes were observed after the UVB treatment. The LST group showed a clear evidence of skin protection compared to the control group (P<0.05). The moisture content, epidermal and horny layer thickness, and protein carbonyl values all revealed that the intake of the lotus seed tea enhanced protection against UVB exposure. As a result, the long-term intake of the lotus seed tea showed the effect of preventing loss of skin moisture, mitigating the formation of abnormal keratinocytes, and contributing to protein oxidation inhibition.