• Title/Summary/Keyword: Cis- and trans-1,3-D

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1,4-Dicyanobutene Bridged Binuclear Iridium (I, III) Complexes and Their Catalytic Activities

  • Park, Hwa-Kun;Chin, Chong-Shik
    • Bulletin of the Korean Chemical Society
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    • v.8 no.3
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    • pp.185-189
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    • 1987
  • Reactions of $Ir(ClO)_4(CO)(PPh_3)_2$ with dicyano olefins, cis-NCCH = CH$CH_2$$CH_2$CN (cDC1B), trans-NCCH = CH$CH_2$$CH_2$CN (tDC1B), trans-NC$CH_2$CH = CH$CH_2$CN (tDC2B), and NC$CH_2$$CH_2$$CH_2$$CH_2$CN (DCB) produce binuclear dicationic iridium (I) complexes, $[(CO)(PPh_3)_2Ir-NC-A-CN-Ir(PPh_3)_2(CO)](ClO_4)_2$ (NC-A-CN = cDC1B (1a), tDC1B (1b), tDC2B (1c), DCB (1d)). Complexes 1a-1d react with hydrogen to give binuclear dicationic tetrahydrido iridium (Ⅲ ) complexes, $[(CO)(PPh_3)_2(H)_2Ir-NC-A-CN-Ir(H)_2(PPh_3)_2(CO)](ClO_4)_2$ (NC-A-CN = cDC1B (2a), tDC1B (2b), tDC2B (2c), DCB (2d)). Complexes 2a and 2b catalyze the hydrogenation of cDC1B and tDC1B, respectively to give DCB, while the complex 2c is catalytically active for the isomerization of tDC2B to give cDC1B and tDC1B and the hydrogenation of tDC2B to give DCB at $100^{\circ}C$.

Cis-9, trans-11-Conjugated Linoleic Acid in Dairy Goat Milk was Increased by High Linoleic (Soybean Oil) or Linolenic (Linseed Oil) Acid Diet

  • Choi, Seong-Ho;Kim, Jong-Kyu;Lee, Hong-Gu;Choi, Chang-Weon;Choi, Yang-Il;Song, Man-Kang
    • Food Science of Animal Resources
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    • v.33 no.4
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    • pp.487-492
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    • 2013
  • The objective of this study was to examine the effect of supplementation of high linoleic ($C_{18:2}$) oil or high linolenic ($C_{18:3}$) oil to the diet on milking performance and content of conjugated linoleic acid (CLA) isomers in goat milk fat. Forty five dairy goats (Sumnen, 25 d post-partum, $62.5{\pm}1.2kg$) were randomly assigned to three treatment groups with each group of 15 dairy goats. The goats were fed a basal diet (CON) consisting 1.2 kg concentrate and 1.2 kg chopped hay (0.6 chopped alfalfa and 0.6 kg hay) daily with 4% soybean oil (SO) or 4% linseed oil (LO). Daily feed intake was not influenced (p>0.05) but daily milk yield (p<0.001) and milk fat yield (p<0.001) were significantly increased by supplementation of oils. Supplementation of oils decreased the short chain fatty acid, medium-chain fatty acid and saturated fatty acid in goat milk fat while increased trans vaccenic acid (trans-11-$C_{18:1}$, TVA), oleic acid ($C_{18:1}$), $C_{18:2}$, $C_{18:3}$, cis-9, trans-11-CLA (c9, t11-CLA), trans-10, cis- 12-conjugated linoleic acid (t10, c12-CLA), unsaturated fatty acids, mono unsaturated fatty acid and long-chain fatty acid in goat milk fat (p<0.001). Especially, c9, t11-CLA, t10, c12-CLA and ${\omega}-3$ fatty acid ($C_{18:3\;n-3}$) in milk fat were highest when goat fed LO diet. Based on the result, it is suggested that supplementation of linseed oil should be an effective method to increase CLA isomers and ${\omega}-3$ fatty acid in goat milk fat without negative effect on lactating performance.

Performance, Carcass Quality and Fatty Acid Profile of Crossbred Wagyu Beef Steers Receiving Palm and/or Linseed Oil

  • Suksombat, Wisitiporn;Meeprom, Chayapol;Mirattanaphrai, Rattakorn
    • Asian-Australasian Journal of Animal Sciences
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    • v.29 no.10
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    • pp.1432-1442
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    • 2016
  • The objective of this study was to determine the effect of palm and/or linseed oil (LSO) supplementation on carcass quality, sensory evaluation and fatty acid profile of beef from crossbred Wagyu beef steers. Twenty four fattening Wagyu crossbred beef steers (50% Wagyu), averaging $640{\pm}18kg$ live weight (LW) and approximately 30 mo old, were stratified and randomly assigned in completely randomized design into 3 treatment groups. All steers were fed approximately 7 kg/d of 14% crude protein concentrate with ad libitum rice straw and had free access to clean water and were individually housed in a free-stall unit. The treatments were i) control concentrate plus 200 g/d of palm oil; ii) control concentrate plus 100 g/d of palm oil and 100 g/d of LSO, iii) control concentrate plus 200 g/d of LSO. This present study demonstrated that supplementation of LSO rich in C18:3n-3 did not influence feed intakes, LW changes, carcass and muscle characteristics, sensory and physical properties. LSO increased C18:3n-3, C22:6n-3, and n-3 polyunsaturated fatty acids (PUFA), however, it decreased C18:1t-11, C18:2n-6, cis-9, trans-11, and trans-10,cis-12 conjugated linoleic acids, n-6 PUFA and n-6:n-3 ratio in Longissimus dorsi and Semimembranosus muscles.

Synthesis, Characterization, and Crystal Structures of Iron(Ⅱ) and Manganese(II) Complexes with 4,7-bis(2-pyridylmethyl)-1-thia-4,7-diazacyclononane

  • Delong Zhang;Daryle H. Busch;Nathaniel W. Alcock
    • Bulletin of the Korean Chemical Society
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    • v.19 no.9
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    • pp.897-906
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    • 1998
  • A new synthesis has been developed for 1-thia-4,7-diazacyclononane and the complexation behavior of a particular derivative has been explored. The pentadentate ligand 4,7-bis(2-pyridylmethyl)-l-thia-4,7-diazacyclononane ([9]$N_2SPY_2$) and its iron(Ⅱ) and manganese(Ⅱ) complexes were prepared and characterized. Magnetic moments of 5.17 and 5.90 μB respectively, indicate that the iron(Ⅱ) and manganese(Ⅱ) complexes are high spin. Charge transfer transitions (d-π*) occur for [Fe(Ⅱ)([9]$N_2SPY_2)(X)]^{n+}$at 27027, 25000, and 24390 cm-1 for X=$H_2O$, Cl-, and OH-, respectively. In acetonitrile solution, the cyclic voltammogram of the manganese(Ⅱ) complex exhibits a redox couple at 0.92 V vs. NHE while the redox potentials for [Fe(Il)([9]$N_2SPY_2)(X)]^{n+}$ are 0.70, 0.66, and 0.37 V vs. NHE for X=$H_2O$, Cl-, and OH-, respectively. The d-π* charge transfer energy and Fe(Ⅱ)/Fe(Ⅲ) redox potential for [Fe(Ⅱ)([9]$N_2SPY_2)(X)]^{n+}$ increase in the same order: $H_2O>Cl^- >OH^-$. The crystal structures of the iron(Ⅱ) and manganese(Ⅱ) complexes reveal that the metal ions are sixcoordinate, binding to four nitrogen atoms and a sulfur atom from the pentadentate ligand, as well as a chloride anion, with the chloride and sulfur atoms in cis positions. The two metals have similar coordination geometries, which are closer to trigonal prismatic than octahedral. In both iron and manganese complexes, the M-N($sp_3$) trans to Cl- is 0.07 Å longer than the one cis to Cl- , and M-N($sp^2$) trans to S is 0.05 longer than the one cis to S atom.

Effects of Linseed Oil or Whole Linseed Supplementation on Performance and Milk Fatty Acid Composition of Lactating Dairy Cows

  • Suksombat, Wisitiporn;Thanh, Lam Phuoc;Meeprom, Chayapol;Mirattanaphrai, Rattakorn
    • Asian-Australasian Journal of Animal Sciences
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    • v.27 no.7
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    • pp.951-959
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    • 2014
  • The objective of this study was to determine the effects of linseed oil or whole linseed supplementation on performance and milk fatty acid composition of lactating dairy cows. Thirty six Holstein Friesian crossbred lactating dairy cows were blocked by milking days first and then stratified random balanced for milk yields and body weight into three groups of 12 cows each. The treatments consisted of basal ration (53:47; forage:concentrate ratio, on a dry matter [DM] basis, respectively) supplemented with 300 g/d of palm oil as a positive control diet (PO), or supplemented with 300 g/d of linseed oil (LSO), or supplemented with 688 g/d of top-dressed whole linseed (WLS). All cows were received ad libitum grass silage and individually fed according to the treatments. The experiment lasted for 10 weeks including the first 2 weeks as the adjustment period, followed by 8 weeks of measurement period. The results showed that LSO and WLS supplementation had no effects on total dry matter intake, milk yield, milk composition, and live weight change; however, the animals fed WLS had higher crude protein (CP) intake than those fed PO and LSO (p<0.05). To compare with the control diet, dairy cow's diets supplemented with LSO and WLS significantly increased milk concentrations of cis-9,trans-11-conjugated linoleic acid (CLA) (p<0.05) and n-3 fatty acids (FA) (p<0.01), particularly, cis-9,12,15-C18:3, C20:5n-3 and C22:6n-3. Supplementing LSO and WLS induced a reduction of medium chain FA, especially, C12:0-C16:0 FA (p<0.05) while increasing the concentration of milk unsaturated fatty acids (UFA) (p<0.05). Milk FA proportions of n-3 FA remarkably increased whereas the ratio of n-6 to n-3 decreased in the cows supplemented with WLS as compared with those fed the control diet and LSO (p<0.01). In conclusion, supplementing dairy cows' diet based on grass silage with WLS had no effect on milk yield and milk composition; however, trans-9-C18:1, cis-9,trans-11-CLA, n-3 FA and UFA were increased while saturated FA were decreased by WLS supplementation. Therefore, it is recommended that the addition 300 g/d of oil from whole linseed should be used to lactating dairy cows' diets.

DFT Study for Substitution Patterns of C20H18X2 Regioisomers (X = F, Cl, Br, or OH)

  • Hwang, Yong-Gyoo;Lee, Seol;Lee, Kee-H.
    • Bulletin of the Korean Chemical Society
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    • v.33 no.2
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    • pp.641-646
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    • 2012
  • We used the hybrid density-functional (B3LYP/6-31G(d,p)) method to analyze the substitution patterns of $C_{20}H_{18}X_2$ derivatives (X = F, Cl, Br, or OH) obtained as disubstituted $C_{20}H_{20}$ cages. Our results suggest that the cis-1 regioisomers (1,2-dihalo derivatives) are less stable than the trans-1 regioisomers (1,20-dihalo derivatives), whereas in the case of the dihydroxy derivatives, the cis-1 regioisomer is more stable than the trans-1 regioisomer. This implies that in the dihalo-induced strain cages of $C_{20}H_{18}X_2$, the strain effect would affect the relative energies, while in the dihydroxide, the hydrogen bonds have a stronger effect on the relative energies in cis-1 regioisomer than the strain effect do. Thus this supports the experimental result in which the bisvicinal tetrol was of particular preparative-synthetic interest as a substitute for the lacking bisvicinal tetrabromide. Further, the topologies of the HOMO and LUMO characteristics of all $C_{20}H_{18}Cl_2$ and $C_{20}H_{18}Br_2$ regioisomers with the same symmetry are same, but they are different from those of $C_{20}H_{18}F_2$ and $C_{20}H_{18}(OH)_2$. This indicates that the five regioisomers of each $C_{20}H_{20}$ disubstituted derivative will have an entirely different set of characteristic chemical reactions.

Comparison of Essential Oil Composition of Artemisia iwayomogi and Artemisia capillaris (더위지기와 사철쑥의 정유성분 조성 비교)

  • Hong, Chul-Un
    • Applied Biological Chemistry
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    • v.47 no.1
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    • pp.124-129
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    • 2004
  • The composition of essential oils isolated from the aerial parts of Artemisia iwayomogi Kitamura and Artemisia capillaris Thunberg collected from two diffenent cultivation area, respectively, was analyzed by GC and GC-MS. Sixty components were identified in oils from A. iwayomogi. The major components of A. iwayomogi oil collected from one area (Sample A) were iso-pinocamphone (31.64%), 1,8-cineo1e (21.55%), ${\beta}-pinene$ (4.46%), pinocarvone (3.72%), myrtenal (3.42%) and trans-pinocarve1 (3.14%), and the major components of the oil from the other area (Sample B) were camphor (26.99%), 1,8-cineo1e (21.55%), ${\alpha}-terpineol$ (7.63%), borneol (4.10%), camphene (3.97%) and artemisia ketone (3.84%). Eighty components were identified in oils from A. capillaris. The major components were capillene $(26.01{\sim}30.31%)$, ${\beta}-pinene(8.55{\sim}18.38%)$, ${\beta}-caryophyllene(8.80{\sim}13.70%)$, ${\beta}-himachalene(1.67{\sim}5.57%)$, $cis,trans- {\alpha}-farnesene(2.10{\sim}7.38%)$ and germacrene D $(2.27{\sim}5.46%)$ and there was no difference in oil composition of A. capillaris between two cultivation area.

Spectroscopic Characterization of Soil Humic Acid Fractions by Molecular Weight (토양에서 추출한 흄산의 분자량별 분류에 따른 분광학적 성질 비교)

  • Shin, Hyun Sang;Moon, Hichung;Yang, Han Beom;Yun, Sock Sung
    • Journal of the Korean Chemical Society
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    • v.39 no.1
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    • pp.66-70
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    • 1995
  • The soil humic acid was subdivided into four subfractions by molecular weight (F1: >100.000 dalton; F2: >100.000 dalton; F3: >10.000 dalton; F4: >2.000 dalton) using MP-dual hollow fiber ultrafiltration system. The characterization using IR, 1H and 13C NMR spectroscopy, showed similar spectroscopic features of HA, demonstrating that the bulk properties of HA subfractions are very similar to one another. IR spectral data showed a decrease in polysaccharide contents and increase in carboxylate functionality as molecular weight become smaller.functions. The structure of (NO) can be described by two interactions (N${\cdot}{\cdot}{\cdot}$N, N${\cdot}{\cdot}{\cdot}$O). One is the ONNO structure with an (N${\cdot}{\cdot}{\cdot}$N) interaction. In this structure, acyclic cis-ONNO with $C_{2v}$-symmetry, acyclic trans-ONNO with $C_{2h}$, and cyclic ONNO with trapezoidal structure ($C_{2v}$) are optimized at the MP2 level. The other structure is the ONON structure with an (N${\cdot}{\cdot}{\cdot}$O) interaction. In the structure, acyclic cis-ONON with Cs$^{-symmetry}$ and cyclic ONON of the rectangular ($C_{2h}$), square $(D_{2h})$, rhombic $(D_{2h})$, and parallelogramic $(D_{2h})$ geometries are also optimized. It is found that acyclic cis-ONNO $(^1A_1$) is the most stable structure and cyclic ONNO ($^3A_1$) is the least stable. Acyclic trans-ONNO ($^3A_1$) with an (N${\cdot}{\cdot}{\cdot}$N) interaction, acyclic trans-ONON and bicyclic ONON $(C_{2v})$ with (N${\cdot}{\cdot}{\cdot}$O) interaction, and acyclic cis- and trans-NOON with an (O${\cdot}{\cdot}{\cdot}$O) interaction can not be optimized at the MP2 level. Particularly, acyclic trans-ONNO with $C_{2h}$-symmetry can not be optimized at the CCSD(T) level. Meanwhile, acyclic NNOO ($^1A_1$, $C_s)$ and trianglic NNOO ($^1A_1$,$C_{2v})$ formed by the (O${\cdot}{\cdot}{\cdot}$N) interaction between $O_2$and $N_2$are optimized at the MP2 level. The binding energies and the relative energy gaps among the isomers are found to be relatively small./sec. Spiral CT scans during the arterial phase were obtained 35 seconds after the injection of contrast medium. CT findings of 78 lesions less than 4cm in diameter were correlated with angiographic findings. Results : The attenuation of lesions was high(n = 69), iso(n = 5), and low(n = 4) compared with liver parenchyma during the arterial phase of spiral CT. In lesions with high-, iso-, and low-attenuation during the arterial phase of spiral CT, hypervascularity on angiograms was found in 63 of 69(91.3%), three of five(60%), and three of four lesions(75%), respectively. Six lesions with high-attenuation on the arterial phase of spiral CT were not seen on angiography. Two iso-attenuated and one low-attenuated lesion were hypovascular on angiograms. Conclusion : The results of this study suggest that with some exceptions there was good correlation between the arterial phase of spiral CT and angiography.

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Asymmetric Intramolecular Diels-Alder Cycloadditions of 2-Pyrone-3-Carboxylates and Synthesis of Vitamin $D_3$ A Ring Phosphine Oxide

  • 조천규;Gary H. Posner
    • Bulletin of the Korean Chemical Society
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    • v.19 no.9
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    • pp.957-961
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    • 1998
  • Intramolecular Diels-Alder cycloadditions of 2-pyrone-3-carboxylates with trans-vinyl silaketal groups tethered via a chiral, non-racemic 1,3-butanediol auxiliary proceeded in unexpected stepwise cycloadditions through ionic intermediates to provide cis-disubstituted bicylolactones. The ratio of two isomers, exo and endo, was 5 to 1, and each isomer was found to be diastereomerically pure (>99% de). Their relative and absolute stereochemistries were determined by $^1H$ NMR spectroscopy and confirmed by X-ray crystallography of minor, endo-adduct 9. The major exo-adduct was successfully transformed to (-)-2-butyl substituted A-ring phophine oxide 16, a key element for the synthesis of 2-butyl vitamin D3.

Synergistic Utilization of Dichloroethylene as Sole Carbon Source by Bacterial Consortia Isolated from Contaminated Sites in Africa

  • Olaniran, Ademola O.;Mfumo, Nokukhanya H.;Pillay, Dorsamy;Pillay, Balakrishna
    • Biotechnology and Bioprocess Engineering:BBE
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    • v.11 no.3
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    • pp.205-210
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    • 2006
  • The widespread use and distribution of chloroethylene organic compounds is of serious concern owing to their carcinogenicity and toxicity to humans and wildlife. In an effort to develop active bacterial consortia that could be useful for bioremediation of chloroethylene-contaminated sites in Africa, 16 combinations of 5 dichloroethylene (DCE)-utilizing bacteria, isolated from South Africa and Nigeria, were assessed for their ability to degrade cis- and trans- DCEs as the sole carbon source. Three combinations of these isolates were able to remove up to 72% of the compounds within 7 days. Specific growth rate constants of the bacterial consortia ranged between 0.465 and $0.716\;d^{-1}$ while the degradation rate constants ranged between 0.184 and $0.205\;d^{-1}$ with $86.36{\sim}93.53\;and\;87.47{\sim}97.12%$ of the stoichiometric-expected chloride released during growth of the bacterial consortia in cis- and trans-DCE, respectively. Succession studies of the individual isolates present in the consortium revealed that the biodegradation process was initially dominated by Achromobacter xylosoxidans and subsequently by Acinetobacter sp. and Bacillus sp., respectively. The results of this study suggest that consortia of bacteria are more efficient than monocultures in the aerobic biodegradation of DCEs, degrading the compounds to levels that are up to 60% below the maximum allowable limits in drinking water.