• Title/Summary/Keyword: isomers

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Synthesis and Characterization of C-meso and C-racemic Isomers of a Reinforced Tetraaza Macrocycle and Their Copper(II) Complexes

  • Jeong, Gyeong Rok;Kim, Juyoung;Kang, Shin-Geol;Jeong, Jong Hwa
    • Bulletin of the Korean Chemical Society
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    • v.35 no.7
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    • pp.2043-2048
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    • 2014
  • Two isomers of a new tetraaza macrotricycle 2,2,4,9,9,11-hexaazamethyl-1,5,8,12-tetraazatricyclo[$10.2.2^{5.8}$]-octadecane ($L^2$) containing additional N-$CH_2CH_2$-N linkages, C-meso-$L^2$ and C-racemic-$L^2$, have been prepared by the reaction of 1-bromo-2-chloroethane with C-meso-$L^1$ or C-racemic-$L^1$ ($L^1$ = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). Both C-meso-$L^2$ and C-racemic-$L^2$ react with copper(II) ion to form $[Cu(C-meso-L^2)]^{2+}$ or $[Cu(C-racemic-L^2)]^{2+}$ in dehydrated ethanol, but do not with nickel(II) ion under similar conditions. Crystal structure of [Cu(C-racemic-$L^2$)($H_2O$)]$(ClO_4)_2$ shows that the complex has distorted square-pyramidal coordination geometry with an apically coordinated water molecule. Unexpectedly, the Cu-N distances [2.016(3)-2.030(3) ${\AA}$] of [Cu(C-racemic-$L^2$)($H_2O$)]$(ClO_4)_2$ are longer than those [1.992(3)-2.000(3) ${\AA}$] of [Cu(C-racemic-$L^1$)($H_2O$)]$(ClO_4)_2$. As a result, $[Cu(C-racemic-L^2)(H_2O)]^{2+}$ exhibits weaker ligand field strength than $[Cu(C-racemic-L^1)(H_2O)]^{2+}$. The copper(II) complexes readily react with CN- ion to yield the cyano-bridged dinuclear complex $[Cu_2(C-meso-L^2)_2CN]^{3+}$ or $[Cu_2(C-racemic-L^2)_2CN]^{3+}$. Spectra and chemical properties of $[Cu(C-meso-L^2)]^{2+}$ and $[Cu_2(C-meso-L^2)_2CN]^{3+}$ are not quite different from those of $[Cu(C-racemic-L^2)]^{2+}$ and $[Cu_2(C-racemic-L^2)_2CN]^{3+}$, respectively.

Changes of Volatile Components in Alaska Pollack Sik-hae during Low-Temperature Fermentation (전통 명태식해 저온숙성 중 휘발성 성분의 변화)

  • Cha, Yong-Jun;Jeong, Eun-Jeong;Kim, Hun;Lee, Young-Mi;Cho, Woo-Jin
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.31 no.4
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    • pp.566-571
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    • 2002
  • Volatile flavor compounds in Alaska pollack sik-hae during fermentation at 5$^{\circ}C$ were analyzed by liquid-liquid continuous extraction (LLCE) and gas chromatography/mass spectrometry (GC/MS) methods. Sixty five volatile compounds were detected in Alaska pollack sik-hae during fermentation. These compounds were composed mainly of 11 S-containing compounds, 13 alcohols, 13 acids, 4 aldehydes, 4 ketones, 6 terpenes,4 aromatic compounds and 10 miscellaneous compounds. Among these, 9 S-containing compounds (3-(methylthio)-1-propene, dimethyl disulfide, diallyl sulfide, methylallyl disulfide, methyl-(E) -propenyl disulfide, dimethyl trisulfide, 2 diallyl disulfide isomers and diallyl trisulfide), 2 acids (acetic acid and butanoic acid), 2 ketones (2, 3-butanedione and 6-methyl-5-hepten-2-one) and 2 esters (ethyl formate and ethyl acetate) were significantly increased during fermentation (p<0.05), and these compounds were suspected to affect on the odor of Alaska pollack sik-hae.

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.

Analysis and Comparison of Cerebroside Components from Soybean Fermented Foods (대두발효식품 Cerebroside의 구성성분 분석 및 비교)

  • 이은열;김희숙
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.31 no.2
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    • pp.177-183
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    • 2002
  • Cerebroside fatty acids, sugars and long-chain sphingoid bases in raw soybean and soybean fermented foods (chongkukjang and deunjang) were analyzed using gas chromatography-mass spectrometry (GC-MS) and high-pH anion exchange chromatography with pulsed amerometric detection (HPAEC-PAD). Fatty acids of acid-hydrolyzed cerebrosides were derivatized to O-TMS methylester and analysed. The major fatty acids in raw soybean and chongkukjang cerebrosides were identified as 2-hydroxyhexadecanoic acid (16 : 0h), 2-hydroxydocosanoic acid (22 : 0h) and 2-hydroxytetracosanoic acid (24 : 0h). In the case of deunjang cerebroside, 24 : 0h (40.9%) and 22 : 0h (23.4%) were major fatty acids, but 16 : 0h, 23 : 0h, 25 : 0h and 26 : 0h were also detected. Long-chain sphingoid bases of acid-hydrolyzed cerebrosides from raw soybean, chongkukjang and deunjang consisted primarily of 4-tracts, 8-tracts-sphingadienine (dihydroxy base, d18 : 2$\Delta$$^{4trans, 8trans}$) and sis-tracts isomers of 4-hydroxy-sphingenine (trihydroxy base, tl8:1$\Delta$$^{4trans or cis}$) with much less amounts of phytosphingosine (tl8: 0) and isomers of sphingenine (d18 : 1). Although deunjang is a soybean food fermented by fungi and microorganisms for a long period, 2-hydroxyoctadec-3-enoic acid (18 : 1h) and branched 9-methyl-4,8-sphingadienine known as compositional cerebroside fatty acids in Aspergillus species were not detected. Mass spectrum for sugar derivatives in cerebrosides of soybean foods including raw soybean and fermented soybean showed that C-1 of glucose moiety was linked to ceramide backbone as like a monoglucosylceramide.

Optical Resolution of Free Amino Acids with Addition of Copper(II) Chelates in a Reversed-Phase Liquid Chromatography (구리(II) 킬레이트의 첨가에 의한 자유아미노산 광학이성질체의 역상 액체크로마토그래피적 분리)

  • Sun Haing Lee;Tae Sub Oh;Hong Yeup An;Kyung Sug Park;Sang Oh OH
    • Journal of the Korean Chemical Society
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    • v.36 no.6
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    • pp.879-888
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    • 1992
  • Separation of the optical isomers of free amino acids by a reversed phase high performance liquid chromatography has been studied by adding a copper(II) complex of L-proline or L-proline derivatives (hydroxy-L-proline, N-benzyl-L-proline, p-xylenyl-L-proline, p-xylenyl-hydroxy-L-proline) in the mobile phase. An OPA postcolumn detection system was used for the detection of amino acids. The chromatographic properties for the free amino acids were discussed in terms of the pH, the kinds and concentration of chelate or organic modifier. The retention behaviors of the free amino acids were considerably different from, those of DNS-amino acids or DABS-amino acids. The enantioselectivity of the free amino acids was better than that of derivatized amino acids. The enantioselectivity between the optical isomers observed by use of the Cu(II)-p-xylenyl-L-proline chiral cheleate was the best among the several copper(II) chelate. A separation mechanism could be illustrated not only by the hydrophobic interaction of the diastereomer with stationary phase but also by the steric effect of the ligand exchange reaction between the free-amino acids and copper chelate.

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BHC Residues in Brown Rice Produced in Korea (한국산 현미(玄米)중 BHC의 잔류성(殘留性) 연구(硏究))

  • Kim, Yong-Hwa;Song, Ki-Joon;Lee, Su-Rae
    • Korean Journal of Food Science and Technology
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    • v.10 no.3
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    • pp.306-312
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    • 1978
  • Residue levels of an organochlorine insecticide, BHC, were determined for brown rice samples produced in Korea by collection and field experiments to obtain the following results. 1) Residue levels of total BHC in 112 samples (an Indica type variety Tongil) produced in 1976 and collected from 9 provinces in proportion to the production level of rice ranged from 0.0010 to 0.0762 ppm, the average being 0.0061 ppm. 2) The residue levels in samples from Jeonbook, Kyongnam and Choongnam provinces were higher than the average for whole samples. BHC isomers were found in the order of ${\alpha}>{\gamma}>{\beta}>{\delta}$ isomers, and the detection frequency by range were 89.3% below 0.01 ppm, 9.8% for $0.01{\sim}0.05{\;}ppm$ and 0.9% for $0.05{\sim}0.10{\;}ppm$. 3) In field experiments according to conventional agronomical practices, the brown rice samples after spraying of BHC at the first generation time of rice stem borer (4 kg of 6% granular formulation/10 a paddy field) showed a little higher residue level than control samples, but not more than 0.035 ppm, whereas samples after spraying at the second generation time (3 kg/10 a) contained in the range of $0.04{\sim}0.19\;ppm$.

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Effect of Substituted Groups on the Retention of Monosubstituted Phenols in Reversed-Phase Liquid Chromatography (역상 액체 크로마토그래피에서 페놀 일치환체들의 머무름에 미치는 치환기들의 영향)

  • Kim, Hun Ju;Lee, In Ho;Lee, Dae Un
    • Journal of the Korean Chemical Society
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    • v.38 no.8
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    • pp.562-569
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    • 1994
  • The retention data of twenty one monosubstituted phenols in the eluent systems containing 30∼70% of methanol or acetonitrile as organic modifiers, on $ C_{18}$ and Phenyl columns were collected to investigate the effect of the substituted groups on the retention of phenols. The capacity factors of the solutes except amino phenols are greater on $ C_{18}$ than on Phenyl column. And all the solutes have shown greater capacity factors in methanol-water than that in acetonitrile-water as a mobile phase. Generally the elution order between meta and para isomers of monosubstituted phenols in consistent (p < m) regardless of the polarity of the substituted group. But the elution order between ortho and meta isomers of phenol varies with regard to the polarity of the substituted group. The retention of the monosubstituted phenols has been influenced by the interaction between the solute and unreacted silanol of columns as well as the interaction between the solute and $ C_{18}$ or phenyl group of columns. And then, the effect of unreacted silanol on the retention of the monosubstituted phenols is greater on $ C_{18}$ than on Phenyl column. And the greater hydrogen bonding acceptor basicity(${\beta}$) of the substituted group is, the greater this effect is. The relationship between the retention of the monosubstituted phenols and their parameters such as van der Waals volume(VWV) and hydrogen bonding acceptor basicity(${\beta}$) has been investigated. The good linearity has been observed in the plot log k' vs. (1.01VWV/100-1.84${\beta}$). In consequence, the retention of the monosubstituted phenols on $ C_{18}$ and Phenyl columns can be easily predicted by the parameter (1.01VWV/100-1.84${\beta}$).

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Synthesis and Properties of Oxygen-bridged Aromatic Polyesters Based on Isomeric Naphthalenediols

  • Park, E-Joon;Park, Bong-Ku;Kim, Jae-Hoon;Lee, Sang-Chul;David J. T. Hill
    • Macromolecular Research
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    • v.8 no.1
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    • pp.12-18
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    • 2000
  • Six aromatic polyesters with ether-linkages were prepared from 4,4'-oxybis(benzoic acid) and naphthalenediol (ND) isomers which were 1,4-, 1,5-, 1,6-, 2,3-, 2,6- and 2,7-derivatives. The solution viscosity numbers ranged from 0.23 to 0.65 dL/g. The glass transition temperatures ranged from 142 to 179$\^{C}$. The initial decomposition temperatures were all above 400$\^{C}$, and the residue weights at 600$\^{C}$ were in the range of 50-64%. Only the polyesters derived from 1,5- and 2,6-NDs, which have a linear linking mode, were found to be semicrystalline and could form thermotropically nematic phase. Multiple melting phenomena and annealing of the polyester derived from 1,5-ND and related polymers are described. The experimental results show that the polyester derived from 1,4-ND of linear shape was amorphous and non-liquid crystalline. Particularly, the polyester derived from 2,3-ND could form a smectic mesophase as banana-shaped molecules, and this is ascribed to the C/sub_2v/ symmetry where highly kinked molecules are packed in the same direction.

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Surfactant enhanced filtration performances of monochlorophenol isomers through low-pressure membrane

  • Kumar, Yogesh;Brahmbhatt, H.;Trivedi, G.S.;Bhattacharya, A.
    • Membrane and Water Treatment
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    • v.2 no.3
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    • pp.137-145
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    • 2011
  • Membrane processes are major breakthrough for the removal of organic pollutants in water remediation. The separations of solutes depend on nature of the membranes and solutes. The separation performance depends on the nature of the solutes (i.e., molecular volume, polarity, and hydrophobicity) for the same membrane. As 4-chlorophenol is of more dipolemoment compared to 2-chlorophenol, the orientation of the molecule enables it pass through the pores of the membrane, which is of negatively charged and thus separation order follows: 2-chlorophenol > 4-chlorophenol. Hydrophobicity factor also supports the order. Addition of sodium dodecyl sulfate (SDS) to chlorophenol solution shows remarkable increase in separation performance of the membrane. The improvement in separation is 1.8 and 1.5 times for 4- and 2- chlorophenol consecutively in case of 0.0082 M SDS (1cmc = 0.0082 M) in the solution. 4-chlorophenol has better attachment tendency with SDS because of its relatively more hydrophobic nature and thus reflects in performance i.e. the separation performance of 4-chlorophenol with SDS through the membrane is better compared to 2-chlorophenol.

Synthesis and Structural Characterization of Transition Metal Complex with N,N'-bis-[2(S) -pyrrolidinylmethyl]phenylene-1,2-diamine (N,N'-Bis[2(S)-2-pyrrolidinylmethyl]phenylene-1,2-diamine를 배위하는 전이금속 착물의 합성 및 구조적 특성)

  • Kim, Dong-Yeub
    • Journal of the Korean Society of Industry Convergence
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    • v.1 no.1
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    • pp.43-49
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    • 1998
  • The SS-phpm 4HCl(N,N'-bis-[2(S)-pyrrolidinylmethyl]phenylene-l,2-diamine-4-Hydrochloride) ligand having stereospecificity has been prepared and reacted with trans-[$Co(pyridine)_4Cl_2]$Cl. The resultants are purple crystals, which are identified to be ${\Delta}$-cis-${\beta}$-[$Co(SS-phpm)Cl_2$]Cl by elemental analysis and UV/Vis- and CD-absorption spectra, The conformation of SS-phpm in ${\Delta}$-cis-${\beta}$ complex is ${\delta}$ ${\varepsilon}$ ${\lambda}$ (SSSS) for each of the five-membered chelated ring. Futhermore, according to orientation of secondary amine, total strain energy on each isomers was calculated by molecular mechanics(MM) to verify structural characterization and spectral data. As the result, the most stabilized isomer was ${\Delta}$-cis-${\beta}$(SSSS). The value of total strain energy(U) of ${\Delta}$-cis-${\beta}$(SSSS) isomer was 63.21 kcal/mol, respectively.

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