• Title/Summary/Keyword: ${\alpha},{\beta}-unsaturated\

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Kinetics and Mechanism of Alkalie Hydrolysis of Cinnamonitrile (II) (Cinnamonitrile의 알카리 가수분해(加水分解) 반응(反應)메카니즘 (II))

  • Sung, Nack Do;Chung, Woo Jin;Kwon, Ki Sung;Park, Byung Kwan
    • Korean Journal of Agricultural Science
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    • v.10 no.2
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    • pp.354-364
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    • 1983
  • Confonmation of (Z)-cinnamonitrile have been studied by molecular orbital theoretically using extended Huckel theory(EHT) and CNDO/2 molecular orbital calculation methods. The results indicate that the stability of conformation is(Z)-gauch>(Z)-planar. The rate constants for alkalie hydrolysis of cinnamonitrile at pH 7.0-14.0 range have been determined by ultra-violet spectrophotometry in 50% methanol at $25^{\circ}C$ and the following rate equation which can be applied over wide pH range was obtained; $${\therefore}k=({\frac{1.41{\times}10^{-14}+1.21{\times}10^7/[H_3O^+]}{2.65{\times}10^{-7}+1.64/[H_3O^+]})+9.14{\times}10^9/[H_3O^+]$$ The rate equation reveals that, at pH 7.0-10.0, the reaction is initiated by the addition of water molecule to unsaturated cabon-carhon double bond of cinnamonitrile and ${\alpha}C-{\beta}C$ bond scission follow subsequently in neutral and alkalie media. At pH 12.0-14.0, in strong alkalie solution, that so-called Michael type nucleophilic addition that the over-all rate constants is only dependent upon the concentration of hydroxide ion occurs competitively and are very complicated. Hence, the reaction mechanism of alkalie hydrolysis of cinnamonitrile which did not carefully before can be fully explained.

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AMPKα, C/EBPβ, CPT1β, GPR43, PPARγ, and SCD Gene Expression in Single- and Co-cultured Bovine Satellite Cells and Intramuscular Preadipocytes Treated with Palmitic, Stearic, Oleic, and Linoleic Acid

  • Choi, S.H.;Park, S.K.;Johnson, B.J.;Chung, K.Y.;Choi, C.W.;Kim, K. H.;Kim, W.Y.;Smith, S.B.
    • Asian-Australasian Journal of Animal Sciences
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    • v.28 no.3
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    • pp.411-419
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    • 2015
  • We previously demonstrated that bovine subcutaneous preadipocytes promote adipogenic gene expression in muscle satellite cells in a co-culture system. Herein we hypothesize that saturated fatty acids would promote adipogenic/lipogenic gene expression, whereas mono- and polyunsaturated fatty acids would have the opposite effect. Bovine semimembranosus satellite cells (BSC) and intramuscular preadipocytes (IPA) were isolated from crossbred steers and cultured with 10% fetal bovine serum (FBS)/Dulbecco's Modified Eagle Medium (DMEM) and 1% antibiotics during the 3-d proliferation period. After proliferation, cells were treated for 3 d with 3% horse serum/DMEM (BSC) or 5% FBS/DMEM (IPA) with antibiotics. Media also contained $10{\mu}g/mL$ insulin and $10{\mu}g/mL$ pioglitazone. Subsequently, differentiating BSC and IPA were cultured in their respective media with $40{\mu}M$ palmitic, stearic, oleic, or linoleic acid for 4 d. Finally, BSC and IPA were single- or co-cultured for an additional 2 h. All fatty acid treatments increased (p = 0.001) carnitine palmitoyltransferase-1 beta ($CPT1{\beta}$) gene expression, but the increase in $CPT1{\beta}$ gene expression was especially pronounced in IPA incubated with palmitic and stearic acid (6- to 17-fold increases). Oleic and linoleic acid decreased (p = 0.001) stearoyl-CoA desaturase (SCD) gene expression over 80% in both BSC and IPA. Conversely, palmitic and stearic acid increased SCD gene expression three fold in co-cultured in IPA, and stearic acid increased $AMPK{\alpha}$ gene expression in single- and co-cultured BSC and IPA. Consistent with our hypothesis, saturated fatty acids, especially stearic acid, promoted adipogenic and lipogenic gene expression, whereas unsaturated fatty acids decreased expression of those genes associated with fatty acid metabolism.

Selective Reduction with Lithium Borohydride. Reaction of Lithium Borohydride with Selected Organic Compounds Containing Representative Functional Groups (수소화붕소리튬에 의한 선택환원. 수소화붕소리튬과 대표적 유기화합물과의 반응)

  • Nung Min Yoon;Jin Soon Cha
    • Journal of the Korean Chemical Society
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    • v.21 no.2
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    • pp.108-120
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    • 1977
  • The approximate rates and stoichiometries of the reaction of lithium borohydride, with fifty two selected organic compounds containing representative functional groups under the standard condition (tetrahydrofuran, $0^{\circ}$), were studied.Among the active hydrogen compounds,primary alcohols and compounds containing an acidic proton liberated hydrogen relatively fast, but secondary and tertiary alcohols very sluggishly. All the carbonyl compounds examined were reduced rapidly within one hour. Especially, among the ${\alpha}{\beta}$-unsaturated carbonyl compounds tested, the aldehydes consumed one hydride cleanly, however the cyclic ketones consumed more than one hydride even at $-20^{\circ}$. Carboxylic acids were reduced very slowly, showing about 60% reduction in 6 days at $25^{\circ}$, however acyl chlorides reduced immediately within 30 minutes. On the other hand, the reductions of cyclic anhydrides proceeded moderately to the hydroxy acid stage, however the further reductions were very slow. Aromatic and aliphatic esters, with exception of the relatively moderate reduction of acetate, were reduced very slowly, however lactones were reduced at a moderate rate. Epoxides reacted slowly, but amides and nitriles as well as the nitro compounds were all inert to this reagent. And cyclohexanone oxime and phenyl isocyanate were reduced very sluggishly. Last of all, all sulfur compounds studied were inert to this hydride.

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NADPH Oxidase and the Cardiovascular Toxicity Associated with Smoking

  • Kim, Mikyung;Han, Chang-Ho;Lee, Moo-Yeol
    • Toxicological Research
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    • v.30 no.3
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    • pp.149-157
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    • 2014
  • Smoking is one of the most serious but preventable causes of cardiovascular disease (CVD). Key aspects of pathological process associated with smoking include endothelial dysfunction, a prothrombotic state, inflammation, altered lipid metabolism, and hypoxia. Multiple molecular events are involved in smoking-induced CVD. However, the dysregulations of reactive oxygen species (ROS) generation and metabolism mainly contribute to the development of diverse CVDs, and NADPH oxidase (NOX) has been established as a source of ROS responsible for the pathogenesis of CVD. NOX activation and resultant ROS production by cigarette smoke (CS) treatment have been widely observed in isolated blood vessels and cultured vascular cells, including endothelial and smooth muscle cells. NOX-mediated oxidative stress has also been demonstrated in animal studies. Of the various NOX isoforms, NOX2 has been reported to mediate ROS generation by CS, but other isoforms were not tested thoroughly. Of the many CS constituents, nicotine, methyl vinyl ketone, and ${\alpha}$,${\beta}$-unsaturated aldehydes, such as, acrolein and crotonaldehyde, appear to be primarily responsible for NOX-mediated cytotoxicity, but additional validation will be needed. Human epidemiological studies have reported relationships between polymorphisms in the CYBA gene encoding p22phox, a catalytic subunit of NOX and susceptibility to smoking-related CVDs. In particular, G allele carriers of A640G and $-930^{A/G}$ polymorphisms were found to be vulnerable to smoking-induced cardiovascular toxicity, but results for C242T studies are conflicting. On the whole, evidence implicates the etiological role of NOX in smoking-induced CVD, but the clinical relevance of NOX activation by smoking and its contribution to CVD require further validation in human studies. A detailed understanding of the role of NOX would be helpful to assess the risk of smoking to human health, to define high-risk subgroups, and to develop strategies to prevent or treat smoking-induced CVD.

Effect of palmitoleic acid on the differentiation of bovine skeletal muscle satellite cells

  • Zhang, Junfang;Li, Qiang;Nogoy, Kim Margarette Corpuz;Sun, Jianfu;Sun, Bin;Wang, Ying;Tang, Lin;Yu, Jia;Jin, Xin;Li, Xiangzi;Choi, Seong-Ho
    • Journal of Animal Science and Technology
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    • v.63 no.4
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    • pp.919-933
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    • 2021
  • We hypothesized that the unsaturated fatty acid palmitoleic acid (POA) could promote the expression of adipogenic/lipogenic genes in bovine skeletal muscle satellite cells (BSCs). The BSCs were cultured in a growth medium containing 10% fetal bovine serum. When the cells reached 80%-90% confluence, we used the differentiation medium with 5% horse serum for differentiation for 96 h. The differentiation medium contained 50 µM, 100 µM and 200 µM POA. Control BSC were cultured only in differentiation media. Compared with the control BSC, the POA BSC significantly up-regulated the expression of paired box 3 (Pax3) and paired box 7 (Pax7) and down-regulated myogenin gene expression (p < 0.01), which indicates a depression in muscle fiber development. However, all POA treatments up-regulated the expression of the adipocyte transcription factors peroxisome proliferator-activated receptor γ (PPARγ), CCAAT/enhancer-binding protein alpha and beta (C/EBP α and C/EBP β), and other genes (p < 0.01) and increased the expression of PAT-family proteins and the concentration of adiponectin in the media. These results indicate that POA can convert part of BSCs into adipocytes.

Thermooxidative Stability of Soybean Oil, Beef Tallow and Palm Oil during Frying of Steamed Noodles (증숙면 튀김 과정 중 대두유, 우지, 팜유의 가열 산화 안정성)

  • Choe, Eun-Ok;Lee, Jin-Young
    • Korean Journal of Food Science and Technology
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    • v.30 no.2
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    • pp.288-292
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    • 1998
  • Thermooxidative stabilities of soybean oil, beef tallow and palm oil were studied during frying of steamed noodles. Steamed noodles were fried in $150^{\circ}C$ oils for 70 sec at the interval of 30 min. The frying oil was taken every 8 hrs for the analysis of peroxide value (PV) and free fatty acid (FFA) content, fatty acid composition, and tocopherol and tocotrienol content. A little change was shown in PV and FFA content in soybean oil during frying; on the other hand, rapid increase in beef tallow and palm oil was observed. Unsaturated fatty acid content was the highest in soybean oil, followed by palm oil and beef tallow. While fatty acid composition in soybean oil was not changed during frying, unsaturated fatty acid content decreased and saturated fatty acid increased in beef tallow and palm oil, which showed susceptibility to the oxidation. The ratio of linoleic acid to palmitic acid did not show difference with frying time in soybean oil: however, it decreased in other oils with a high correlation with frying time and higher decreasing rate in palm oil was observed. These suggested that soybean oil was the most stable to thermooxidation and the stability was followed by beef tallow and palm oil. Tocopherol was disappeared during frying and 87.5, 81.1, and 73.1% were remained in soybean oil after 8, 16 and 24 hour frying, respectively. Also the rate decreased in the order of ${\gamma}-,\;{\beta}-\;and\;{\alpha}-tocopherol$. However, 34.2 and 169.0 ppm tocopherol and tocotrienol which were present in control samples of beef tallow and palm oil were completely disappeared by 8 hr frying. Therefore, high thermooxidative stability of soybean oil resulted from higher residual amount of tocopherol during frying, and lower stability of palm oil than beef tallow was partly due to high degree of unsaturation.

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Synthesis of Binuclear Bismacrocyclic Iron(II) Complex by the Aerobic Oxidation of Iron(II) Complex of 1,4,8,11-Tetraazacyclotetradecane

  • Myunghyun Paik Suh;Gee-Yeon Kong;Il-Soon Kim
    • Bulletin of the Korean Chemical Society
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    • v.14 no.4
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    • pp.439-444
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    • 1993
  • The aerobic oxidation of the Fe(II) complex of 1,4,8,11-tetraazacyclotetradecane, [Fe(cyclam)$(CH_3CN)_2](ClO_4)_2$, in MeCN in the presence of a few drops of $HClO_4$ leads to low spin Fe(III) species [Fe(cyclam)$(CH_3CN)_2](ClO_4)_3$. The Fe(III) cyclam complex is further oxidized in the air in the presence of a trace of water to produce the deep green binuclear bismacrocyclic Fe(II) complex $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$. The Fe(II) ions of the complex are six-coordinated and the bismacrocyclic ligand is extensively unsaturated. $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$ crystallizes in the monoclinic space group $P2_1/n$ with a= 13.099 (1) ${\AA}$, b= 10.930 (1) ${\AA}$, c= 17.859 (1) ${\AA}$, ${\beta}$= 95.315 $(7)^{\circ}$, and Z= 2. The structure was solved by heavy atom methods and refined anisotropically to R values of R= 0.0633 and $R_w$= 0.0702 for 1819 observed reflections with F > $4{\sigma}$ (F) measured with Mo K${\alpha}$ radiation on a CAD-4 diffractometer. The two macrocyclic units are coupled through the bridgehead carbons of ${\beta}$-diimitie moieties by a double bond. The double bonds in each macrocycle unit are localized. The average bond distances of $Fe(II)-N_{imine}$, $Fe(II)-N_{amine}$, and $Fe(II)-N_{MeCN}$ are 1.890 (5), 2.001 (5), and 1.925 (6) ${\AA}$, respectively. The complex is diamagnetic, containing two low spin Fe(II) ions in the molecule. The complex shows extremely intense charge transfer band in the near infrared at 868 nm with ${\varepsilon}$= 25,000 $M^{-1}cm^{-1}$. The complex shows a one-electron oxidation wave at +0.83 volts and two one-electron reduction waves at -0.43 and-0.72 volts vs. Ag/AgCl reference electrode. The complex reacts with carbon monoxide in $MeNO_2$ to form carbonyl adducts, whose $v_{CO}$ value (2010 $cm^{-1}$) indicates the ${\pi}$-accepting property of the present bismacrocyclic ligand.

Comparison of Vitamin E, Phytosterols and Fatty Acid Composition in Commercially Available Grape Seed Oils in Korea (국내 시판 포도씨유의 비타민 E, 식물성스테롤 및 지방산조성 비교)

  • Wie, Min-Jung;Seong, Ji-Hae;Jeon, Keon-Wook;Jung, Heon-Sang;Lee, Jun-Soo
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.37 no.7
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    • pp.953-956
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    • 2008
  • Grape seeds have recently been utilized for the production of seed oil. Grape seed oils (GSOs) are generating increasing interest as a functional food product since it has been shown to contain high levels of vitamin E, unsaturated fatty acids, and phytosterols. The objective of this study was to determine the compositions of vitamin E, fatty acids, and phytosterols in commercially available grape seed oils in Korea. Vitamin E was analyzed by HPLC with fluorometric detector and phytosterol and fatty acid composition was analyzed by GC. GSOs contained total vitamin E in the range of 34.6 to 66.1 mg/100 g oil and high levels of tocotrienols. The GSOs are mainly composed of linoleic acid ranging from 60 to 76%. GSOs also contained $77.0{\sim}166.9\;mg$ of phytosterols/100 g oil.

Nutritional Compositions of Three Traditional Actinidia (Actinidia arguta) Cultivars Improved in Korea (국내에서 개량된 3가지 토종 다래 품종의 영양성분 분석)

  • Jin, Dong Eun;Park, Seon Kyeong;Park, Chang Hyeon;Seung, Tae Wan;Heo, Ho Jin
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.43 no.12
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    • pp.1942-1947
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    • 2014
  • Nutritional compositions of Korean traditional actinidia (Actinidia arguta) cultivars, such as Otumsense, Chiak, and Skinny green, were investigated as high value-added food substances. Among minerals, K content of three cultivars was the highest, and P, Ca, and Na contents were relatively higher than those of other minerals. Contents of essential amino acids were analyzed as follows: Otumsense (198.48 mg/100 g), Chiak (413.50 mg/100 g), and Skinny green (270.07 mg/100 g). Total amino acids of Chiak were the highest among the three cultivars, and major amino acids of the three cultivars were glutamic acid and aspartic acid. Analysis of fatty acids showed that major fatty acids were palmitic acid as a saturated fatted acid and ${\alpha}$-linoleic acid as an unsaturated fatty acid in the three cultivars. Glucose and fructose were major free sugar constituents in the three cultivars. Total free sugar content of Otumsense was relatively higher than others. Finally, niacin and vitamin $B_6$ of Skinny green (1.55 mg/100 g, 1.92 mg/100 g) were the highest among the cultivars. However, ${\beta}$-carotene as a vitamin A precursor ($3.82{\mu}g/100g$) and vitamin C as a natural antioxidant substance (47.18 mg/100 g) of Otumsense cultivar were the highest.

Effects of Dietary Fat Types on Growth Performance, Pork Quality, and Gene Expression in Growing-finishing Pigs

  • Park, J.C.;Kim, S.C.;Lee, S.D.;Jang, H.C.;Kim, N.K.;Lee, S.H.;Jung, H.J.;Kim, I.C.;Seong, H.H.;Choi, Bong-Hwan
    • Asian-Australasian Journal of Animal Sciences
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    • v.25 no.12
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    • pp.1759-1767
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    • 2012
  • This study was performed to determine the effects of dietary fat sources, i.e., beef tallow, soybean oil, olive oil and coconut oil (each 3% in feed), on the growth performance, meat quality and gene expression in growing-finishing pigs. A total of 72 crossbred pigs (Landrace${\times}$Large White${\times}$Duroc) were used at $71{\pm}1$ kg body weight (about 130 d of age) in 24 pens ($320{\times}150$ cm) in a confined pig house (three pigs per pen) with six replicate pens per treatment. The growing diet was given for periods of $14{\pm}3$ d and the finishing diet was given for periods of $28{\pm}3$ d. The fat type had no significant effect either on growth performance or on chemical composition or on meat quality in growing-finishing pigs. Dietary fat type affected fatty acid composition, with higher levels of unsaturated fatty acids (UFAs) and monounsaturated fatty acids (MUFAs) in the olive oil group. Microarray analysis in the Longissimus dorsi identified 6 genes, related to insulin signaling pathway, that were differentially expressed among the different feed groups. Real time-PCR was conducted on the six genes in the longissimus dorsi muscle (LM). In particular, the genes encoding the protein kinase, cAMP-dependent, regulatory, type II, alpha (PRKAR2A) and the catalytic subunit of protein phosphatase 1, beta isoform (PPP1CB) showed the highest expression level in the olive oil group (respectively, p<0.05, p<0.001). The results of this study indicate that the type of dietary fat affects fatty acid composition and insulin signaling-related gene expression in the LM of pigs.