• Title/Summary/Keyword: $C_2H_2,\

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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.

A Study on Basic Investigation for Quality Improvement of Raw-Silk A Study on the Dissolving Behavior of Sericin in the Cocoon Shell and Pupa Protein (Bombyx mori L.) (Part III) (생사 품위향상을 위한 기초조사 연구 견층 Sericin과 용체 단백질의 용해거동에 관한 연구(III))

  • 임영우
    • Journal of Sericultural and Entomological Science
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    • v.17 no.2
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    • pp.161-170
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    • 1975
  • This study is to investigate the content of crude protein intruded in the sericin of cocoon shell and pupa by treatment of buffer solution (pH 1 to pH 13) 20 ml per 1 gram for 30 and 60 minutes at 30$^{\circ}C$, 60$^{\circ}C$ and 100${\pm}$2$^{\circ}C$, respectively. The results obtained are summarized as follows. 1. The quantity of total crude protein obtained from cocoon shell and pupa by treatment during 30 minutes at 30$^{\circ}C$ was dissolved as the largest quantity of 11.874 mg/g at pH 1 and l5.93mg/g at pH 13, but dissolved the smallest quantity 1.75g/g at pH 5 as known. and tile quantity of crude protein treated for 60 minutes is 13.437mg/g at pH 1 and 22.50mg/g at pH 13. Also, the smallest quantity is 2. 813mg/g at pH 5 as known. 2. By the treatment during 30 minutes at 60$^{\circ}C$, the dissolved largest quantity was 13.12mg/g at pH 1 and 21.875 mg/g at pH 13, but the smallest quantity is 2.375mg/g at pH 5 as known After treatment for 60 minutes at 60$^{\circ}C$, the dissolved largest quantity was 17.500 mg/g at pH 1 and 31.56mg/g at pH 13, bu the smallest quantity is 3.849 mg/g at pH 5. 3. The dissolved crude protein from the cocoon shell and pupa by treatment for 30 minutes at 100${\pm}$2$^{\circ}C$ was the largest quantity of 147.000mg/g at pH 1 and 398. 125mg/g at pH 13, but the smallest quantity is 75.00mg/g at pH 5 as known. After treatment for 60 minutes at 100${\pm}$2$^{\circ}C$, the largest quantity was 253.76 mg/g at pH 1 and 460.625mg/g at pH 13, but the smallest quantity is 139.375mg/g at pH 5 as known. 4. The dissolved crude protein from the cocoon shell and pupa was not different in quantity by treatment at 30$^{\circ}C$ or 60$^{\circ}C$. But dissolved crude protein was large quantity from cocoon shell more than pupa, as known. 5. The treatment of cocoon shell and pupa during 60 minutes at 100${\pm}$20$^{\circ}C$ was increased to the dissolved largest quantity of crude protein of 19.20% at pH 1 and 22. 18% at pH 13 from the cocoon shell and 6. 12% at pH, an d 23.87% at pH 13 from the pupa. But dissolved crude protein was increased to the larger quantity from pupa more than cocoon shell.

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MO Studies on $C_{60}$ and Its Pt-Derivatives

  • Lee, Gi Hak;Lee, Han Myeong;Lee, Wang Ro
    • Bulletin of the Korean Chemical Society
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    • v.16 no.3
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    • pp.226-232
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    • 1995
  • The electronic structures of the C60, (H3P)2Pt(η2-C2H4) and (H3P)2Pt(η2-C60) are calculated by using the EHMO method with the fragment analysis. We have modified the EHT parameters so as to yield the orbital energy level correlation and to fit the optical transition gap to the previous theoretical results of C60. In Pt-derivatives, our FMO results with the modified parameters show that the carbon-carbon double bonds of C60 and ethene react like those of electron-poor arenes and alkenes, and also that C60 is more electron-susceptive than C2H4.

Molecular Motions of [N(C2H5)4]+ and [N(CH3)4]+ ions by 1H Nuclear Magnetic Resonance Relaxation in [N(C2H5)4]2CoCl4 and [N(CH3)4]2CoCl4 Single Crystals

  • Yoon, Su-A;Lim, Ae-Ran
    • Journal of the Korean Magnetic Resonance Society
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    • v.15 no.2
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    • pp.146-156
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    • 2011
  • The line widths and spin-lattice relaxation times of protons in $[N(C_2H_5)_4]_2CoCl_4$ and $[N(CH_3)_4]_2CoCl_4$ single crystals were investigated in the temperature range 160-400 K. The temperature dependences of the spin-lattice relaxation times are attributed to the molecular motions of the ethyl and methyl groups in the $[N(C_2H_5)_4]^+$ and $[N(CH_3)_4]^+$ ions respectively. The NMR line widths indicate that the ethyl groups in $[N(C_2H_5)_4]_2CoCl_4$ have one more degree of freedom than the methyl groups in $[N(CH_3)_4]_2CoCl_4$. The experimental results are interpreted in terms of the reorientations of the methyl and ethyl groups.

The Geometrical Isomerization on Acidification in Hexamolybdoheteropoly Oxometalate. The Crystal Structure of $(NH_{4})_{4.5}[H_{3.5}\alpha-PtMo_{6}O_{24}].\;1.5H_{2}O,\;(NH_{4})_{4}[H_{4}\beta-PtMo_{6}O_{24}].\;1.5H_{2}O,\;and\;K_{3.5}[H_{4.5}\alpha-PtMo_{6}O_{24}].\;3H_{2}O$

  • Lee, Uk;Yukiyoshi Sasaki
    • Bulletin of the Korean Chemical Society
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    • v.15 no.1
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    • pp.37-45
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    • 1994
  • $(NH_4)_{4.5}[H_{3.5}{\alpha}-PtMo_6O_{24}]{\cdot}1.5\;H_2O(A),\;(NH_4)_4[H_4{\beta}-PtMo_6O_{24}]{\cdot}1.5\;H_2O(B),\;and\;K_{3.5}[H_{4.5}{\alpha}-PtMo_6O_{24}]{\cdot}3\;H_2O(C)$ have been synthesized and their molecular structures have been also determined by single-crystal X-ray diffraction technique. The space groups, unit cell parameters, and R factors are as follows: Compound A, monoclinic, $A_{2/a}$, a= 19.074 (3), b=21.490 (3), c=15.183 (2) ${\AA};\;{\beta}$=109.67 (1) ${\AA}$; z=8; R=0.075($IF_0I>4{\sigma}(IF_0I);$ Compound B, triclinic, P$bar{1}$, a=10.776 (2), b=15.174 (4), c=10.697 (3) ${\AA};\;{\alpha}$ =126.29 (2), ${\beta}$=111.55 (2), ${\gamma}$=93.18 (2) ${\AA}$; Z=2; R=0.046($IF_0I>3{\sigma}(IF_0I);$): Compound C, triclinic, Pl, a=12.426 (2), b=13.884 (2), c=10.089 (1) ${\AA}$; ${\alpha}$=102.59 (2), ${\beta}$=110.73 (1), ${\gamma}$=53.93 (1) ${\AA}$; Z=2; R=0.074 ($IF_0I>3{\sigma}(IF_0I)$. Compounds A and C contain the well-known Anderson structure (planar structure) heteropoly oxometalate having approximate $bar{3}_m(D_{3d})$ symmetry, while compound B contains the bent structure heteropoly oxometalate having appproximate $2_{mm}(C2_v)$ symmetry. The bent structure and the planar one are geometrical isomers. These compounds are rot only novel heteroply molybdates containing platinate(IV) but also the first example of geometrical isomerism in the hexamolybdoheteropoly oxometalates. That isomerization surprisingly occurred because of the change of only 0.5 non-acidic hydrogen atom attached to the polyanion such as $[H_{3.5}{\alpha} -PtMo_6O_{24}]^{4.5-}{\to}[H_4{\beta}-PtMo_6O_{24}]^{4-}{\to}[H_{4.5}{\alpha} -PtMo_6O_{24}]^{3.5-}$. It seems that the gradual protonation of the polyanion plays an important role in that isomerism. These heteropolyanions form dimers by strong hydrogen bonds between two heteropolyanions in the respective crystal system.

The Crystal and Molecular Structure of Fenothiocarb, $C_{13}H_{19}NO_2S$. (Fenothiocarb, $C_{13}H_{19}NO_2S$의 결정 및 분자구조)

  • 박권일;조성일
    • Korean Journal of Crystallography
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    • v.6 no.2
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    • pp.63-68
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    • 1995
  • The crystal structure of fenothiocarb(S-4-phenoxybutyl dimethylthiocarbamate), C13H19NO2S is monoclinic, space group P21/c, a=9.045(1)Å, b=14.577(2)Å, c=10.727(2)Å, β=103.56(1)°, Z=4, V=1375.20(6)Å3, Dc=1.23g/cm3, λ(Mo-Kα)=0.71069Å, μ=2.3cm-1, F(000)=544, temperature : 293±3K, R=0.049 for 1543 unique observed reflections. The structure was determined by direct method and refined by full-matrix least squares method. The molecules are contacted to the c axis with two fold screw and van der Waales force.

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Salen-Aluminum Complexes as Host Materials for Red Phosphorescent Organic Light-Emitting Diodes

  • Bae, Hye-Jin;Hwang, Kyu-Young;Lee, Min-Hyung;Do, Young-Kyu
    • Bulletin of the Korean Chemical Society
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    • v.32 no.9
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    • pp.3290-3294
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    • 2011
  • The properties of monomeric and dimeric salen-aluminum complexes, [salen(3,5-$^tBu)_2$Al(OR)], R = $OC_6H_4-p-C_6H_6$ (H1) and R = [salen(3,5-$^tBu$)AlOPh]C$(CH_3)_2$ (H2) (salen = N,N'-bis-(salicylidene)-ethylenediamine) as host layer materials in red phosphorescent organic light-emitting diodes (PhOLEDs) were investigated. H1 and H2 exhibit high thermal stability with decomposition temperature of 330 and $370^{\circ}C$. DSC analyses showed that the complexes form amorphous glasses upon cooling of melt samples with glass transition temperatures of 112 and $172^{\circ}C$. The HOMO (ca. -5.2~-5.3 eV) and LUMO (ca. -2.3~-2.4 eV) levels with a triplet energy of ca. 1.92 eV suggest that H1 and H2 are suitable for a host material for red emitters. The PhOLED devices based on H1 and H2 doped with a red emitter, $Ir(btp)_2$(acac) (btp = bis(2-(2'-benzothienyl)-pyridinato-N,$C^3$; acac = acetylacetonate) were fabricated by vacuum-deposition and solution process, respectively. The device based on vacuum-deposited H1 host displays high device performances in terms of brightness, luminous and quantum efficiencies comparable to those of the device based on a CBP (4,4'-bis(Ncarbazolyl) biphenyl) host while the solution-processed device with H2 host shows poor performance.

Effect of UV-C Irradiation on Inactivation of Escherichia coli O157:H7 and Listeria monocytogenes on Washed Carrot during Storage (UV-C 조사가 세척 당근의 저장 중 E. coli O157:H7과 Listeria monocytogenes의 생육저해 및 품질에 미치는 영향)

  • Kim, Ju-Yeon;Kim, Eun-Kyo;Shin, Cho-Long;Song, Kyung-Bin
    • Food Science and Preservation
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    • v.16 no.5
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    • pp.636-643
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    • 2009
  • Inactivation by UV-C irradiation of Escherichia coli O157:H7 and Listeria monocytogenes inoculated onto washed carrots was examined. Carrot samples were inoculated with 6-7 log CFU/mL of E. coli O157:H7 or L. monocytogenes, treated with doses of 0, 1, 3, 5, or $10\;kJ/m^2$ UV-C, and stored at $4{\pm}1^{\circ}C$ for 8 d. The populations of E. coli O157:H7 and L. monocytogenes significantly decreased with increasing irradiation dose (p<0.05). In particular, E. coli O157:H7 and L. monocytogenes populations fell significantly by 2.35 and 2.38 log CFU/g at $10\;kJ/m^2$, respectively, compared to control values. UV-C irradiation inhibited color changes and decreased the whiteness index in carrot during storage, compared to controls. Sensory evaluation results showed that UV-C-treated carrots had better sensory characteristics than did the control. Therefore, the results suggest that UV-C irradiation could be useful to improve the microbial safety and sensory qualities of fresh-cut carrots during storage.

The Effects of Various Reaction Conditions on Trans Isomer Formation in Hydrogenating Edible Soybean Oil (식용(食用) 대두유(大豆油) 경화시(硬化時) 반응조건(反應條件)이 이성체(異性體) 생성(生成)에 미치는 영향(影響))

  • Choi, Eok;Joo, Hyun-Kyu;Lee, Si-Kyung
    • Korean Journal of Food Science and Technology
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    • v.27 no.2
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    • pp.205-209
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    • 1995
  • Edible hardened soybean oil is processed by hydrogenation of refined soybean oil in order to upgrade the heat and oxidation stability and to improve flavor and physical nature. This study aims to investigate the influences of various reaction conditions on iodine value, fatty acid composition and trans isomer formation in hydrogenating soybean oil. In case that hardening temperature is $180^{\circ}C$, trans acid formation increased by 6.2 times more under $3.0{\;}kg/cm^{2}H_{2}$ than under $0.5{\;}kg/cm^{2}H_{2}$, while linolenic acid decreased in contents. In case of $200^{\circ}C$ of hardening temperature trans acid formation showed 4.6% higher under $0.5{\;}kg/cm^{2}H_{2}$ than under $3.0{\;}kg/cm^{2}H_{2}$ while contents of linolenic and linoleic acids showed 0.51% and 2.5% lower respectively. It is concluded that $200^{\circ}C$ of hardening temperature under 0.5 and $3.0{\;}kg/cm^{2}H_{2}$ is better condition because trans isomers are little produced, and iodine value and linolenic acid content decreased in hardening soybean oil.

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Simultaneous Separation and Determination of $^{l4}C\;and\;^3H$ in Spent Resins from PWR Nuclear Power Plants (가압경수로형 원전에서 발생된 폐수지의 $^{14}C$$^3H$ 동시 분리 및 측정)

  • Park, Soon-Dal;Kim, Jung-Suck;Kim, Jong-Goo;Han, Sun-Ho;Jee, Kwang-Yong
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.5 no.3
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    • pp.179-188
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    • 2007
  • In this work $^{14}C\;and\;^3H$ distribution characteristics of spent resins from nuclear power plants(NPPs), pressurized water reactors(PWRs), was investigated. It was found that the recovery percent of $^{14}C$ by the wet oxidation-acid stripping was $81%{\sim}100%$ for the added activity range of $^{14}C,\;0.72\;Bq{\sim}460\;Bq$, and it was not affected by the kinds of stripping acids, 3N-HCl, $3\;N-HNO_3\;and\;3\;N-H_2SO_4$. And the recovery percent of $^3H$ by distillation using the same apparatus was $81%{\sim}101%$ for the added activity range of $^3H,\;0.60\;Bq{\sim}435\;Bq$. Among the tested stripping acids, 3\;N-HCl, $3\;N-HNO_3\;and\;3\;N-H_2SO_4$, only the trapped $^3H$ solution by distillation in $3\;N-H_2SO_4$ was compatible with the 3H scintillator, Ultimagold XR. Neither of the $^{14}C\;and\;^3H$ trapping solutions from the spent ion exchange resin samples by the wet oxidation-3 $N-H_2SO_4$ stripping contained gamma nuclides. However, some gamma nuclides, $^{60}Co,\;^{134}Cs,\;^{137}Cs\;and\;^{54}Mn$, were found in the trapped $^3H$ solutions of the spent resins by the wet oxidation-3 N-HCl stripping. It was the same for the $^3H$ trapping solutions of the spent resins by Sample Oxidizer(PACKARD MODEL 307). Meanwhile only two nuclides, $^{134}Cs,\;and\;^{134}Cs$, were found in the $^{14}C$ trapping solutions of the spent resins by Sample Oxidizer(PACKARD MODEL 307). It was found that most of the $^{14}C$ in the spent resins existed as inorganic carbon form, more than about 70% of the total $^{14}C$ content. Among the analyzed 30 spent ion exchange resin samples, the average concentration of $^{14}C$ and $^3C$ for the high radioactive samples, 8 samples, was $19000\;Bq/g{\pm}41000\;Bq/g,\;670\;Bq/g{\pm}460\;Bq/g$ and that for the low radioactive samples, 22 samples, was $4.2\;Bq/g{\pm}4.3\;Bq/g,\;6.0\;Bq/g{\pm}5.3\;Bq/g$, respectively. And the average $^{14}C/^3H$ ratio for the high radioactive samples, was higher, 28, than that of low radioactive samples, 0.70. Some linear relationship trend was found between the activity concentrations of $^{14}C\;and\;^3H$.

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