• Title/Summary/Keyword: Isomerism

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Synthesis and Characterization of New Polyesters Having Unsaturated Groups from Bis [4-(alkyloxy)benzilidene]succinic Anhydride (Bis[4-(alkyloxy)benzilidene]succinic anhydride로부터 유도된 불포화기를 가지는 새로운 폴리에스터의 합성)

  • 김용석;진왕철;정진철
    • Polymer(Korea)
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    • v.26 no.4
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    • pp.439-444
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    • 2002
  • Several monomeric benzilidene anhydrides (2a~d) haying n-alkyloxy groups with various n-alkyl chain lengths were prepared by Stobbe condensation of diethyl succinate with 4-(n-alkyloxy)benzaldehyde (1a,b) followed by hydrolysis by the succinates and cyclodehydration of the benzilidenated succinic acids. Configurational isomerism of the monomer was investigated by spectroscopic means. It was found that monomers (2a~d) exist in (Z,Z)-isomeric structure. Polymerization was carried out in bulk at 150~$210^{\circ}C$ range in nitrogen flow. The chemical structure and thermal properties of the polymers were characterized by spectroscopic means, TGA and DSC. Their properties highly depended on their chemical structures in accordance with a side chain length.

Multi-Nuclear NMR Investigation of Nickel(II), Palladium(II), Platinum(II) and Ruthenium(II) Complexes of an Asymmetrical Ditertiary Phosphine

  • Raj, Joe Gerald Jesu;Pathak, Devendra Deo;Kapoor, Pramesh N.
    • Journal of the Korean Chemical Society
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    • v.57 no.6
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    • pp.726-730
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    • 2013
  • Complexes synthesized by reacting alkyl and aryl phosphines with different transition metals are of great interest due to their catalytic properties. Many of the phosphine complexes are soluble in polar solvents as a result they find applications in homogeneous catalysis. In our present work we report, four transition metal complexes of Ni(II), Pd(II), Pt(II) and Ru(II) with an asymmetrical ditertiaryphosphine ligand. The synthesized ligand bears a less electronegative substituent such as methyl group on the aromatic nucleus hence makes it a strong ${\sigma}$-donor to form stable complexes and thus could effectively used in catalytic reactions. The complexes have been completely characterized by elemental analyses, FTIR, $^1HNMR$, $^{31}PNMR$ and FAB Mass Spectrometry methods. Based on the spectroscopic evidences it has been confirmed that Ni(II), Pd(II) and Pt(II) complexes with the ditertiaryphosphine ligand showed cis whereas the Ru(II) complex showed trans geometry in their molecular structure.

Temperature-Dependent Redox Isomerism via Intramolecular Electron Transfer. Synthesis and Properties of Co(dmppz)₂(3,6-dbq)₂ (dmppz=1,4-dimethylpiperazine; 3,6-dbq=3,6-di-tert-butyl-1,2-quinone)

  • 정옥상;조두환;박성호;손윤수
    • Bulletin of the Korean Chemical Society
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    • v.18 no.6
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    • pp.628-631
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    • 1997
  • The preparation and characterization of $Co(dmppz)_2(3,6-dbq)_2$ (dmppz=1,4-dimethylpiperazine; 3,6-dbq=3,6-di-tert-butyl-1,2-quinone) are established. Temperature-dependent magnetic moments (100-400 K), variable-temperature IR, and electronic spectra are presented to show that the title complex exhibits an equilibrium via a catechol to cobalt intramolecular electron transfer. At temperatures below 350 K, the charge distribution of the complex is $Co^Ⅲ(dmppz)_2(3,6-dbsq)(3,6-dbcat)$ (3,6-dbsq=3,6-di-tert-butyl-1,2-semiquinonato; 3,6-dbcat=3,6-di-tert-butylcatecholato) whereas at the temperature beyond 390 K, the complex is predominantly Co^Ⅱ(dmppz)_2(3,6-dbsq)_2$ form in the solid state. At the temperature range of 350-390 K a mixture of Co(Ⅲ) and Co(Ⅱ) redox isomers exist at equilibrium. The transition temperature (Tc) of Co(Ⅲ)/Co(Ⅱ) in solution is approximately 50° lower than that in the solid state. In particular, thermal analysis on solid sample of the complex discloses that the transition for the Co(Ⅲ)/Co(Ⅱ) is accompanied by the change in heat content of 12.30 kcal/mol.

Structure and Chemical Reactivity of the Transition Metal Complexes (I). Synthesis and Geometrical Isomerism of the Ethylenediamine-triacetatocobalt (III) Complexes with Ammine or Diamines (전이금속착물의 구조와 그 반응성 (I). 암민류를 포함하는 Ethylenediamine-triacetatocobalt (III) 착물의 합성과 기하이성질현상)

  • Dong-Jin Lee;Bong-Gon Kim;Myung-Ki Doh
    • Journal of the Korean Chemical Society
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    • v.29 no.5
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    • pp.516-521
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    • 1985
  • Ethylenediamine-triacetatocobalt (III) complexes with an ammine, an ethylene-diamine, and a trimethylenediamine as the unidentate ligand were prepared, and were isolated as only one isomer for each case by the Dowex 50W-X8, cation exchange resin in $H^+$ form. The geometrical isomer of these complexes have been assigned cis-equatorial form in the three possible geometrical isomers from the elemental analysis, pH titration, IR, NMR, and electronic absorption spectrum. It was found that $[CoN_3O_3]$ system of the meridional form with multidentate ligand have the first absorption band of the largely splitting pattern, and that the diamines (ethylenediamine, trimethylenediamine) have coordinated to the central cobalt (III) ion as a unidentate ligand.

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Capacity of Oil Cake Ion Exchanger (깻묵 이온교환체의 이온교환능)

  • Dong Won Kim;Hae Young Song;Hwang, Myeong Cheon;Hae Il Ryu
    • Journal of the Korean Chemical Society
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    • v.25 no.5
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    • pp.300-305
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    • 1981
  • The soy bean oil cakes and perillar oil cakes are phosphorylated and sulfonated to be used as ion exchangers. There 40-60mesh cations exchanges have bean tested on the capacity of ion exchange, the adsorption and distribution coefficients of several metal ions in various concentrations of binary solution mixture, hydrochloric acid and alcohol. From there experiments, the following results are concluded. The ion exchange capacity of ion exchangers are higher than 4 meq/g. The adsorption of metal ions on ion exchangers are increased generally as pH is increased, especially Co(II) on sulfonated soy bean oil cake. The distribution coefficients of various metal ions are decreased as the number of branches of carbon and hydroxyl groups are increased. There show that the stereo-isomerism of alkyl group or attraction of ligand have influenced upon various metal ions. Consequently it is deduced that there ion exchanges from soy bean oil cake and perillar oil cake resemble in properties to current ion exchangers.

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Theoretical Study of Flourine Doping Effect on the Y-Ba-Cu-O Superconductor (Y-Ba-Cu-O 초전도체의 불소 도핑효과에 대한 이론적 연구)

  • Choi, U-Sung;Park, Choon-Bae;Song, Min-Jong;Lee, Wang-Ro;Lee, Kee-Hag
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 1993.05a
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    • pp.134-136
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    • 1993
  • Using the extended H$\ddot{u}$ckel molecular orbital method in connection with the tight binding model, we have studied electronic structure and related properties of superconducting $YBa_2Cu_3O_{7-x}$ crystals in which O-atoms in regular sites were selectively replaced with F atoms. The calculations are based on the crystal structure of Y-Ba-Cu-O obtained by Beno et al.. We use atomic coordinates that refer to the unrelaxed Y-Ba-Cu-O system. In analogy to the isomerism problem with molecules, we discuss all possible combinations of F-substitutions in O-sites with one, two, and four F atoms. The calculations are carried out within charged clusters model for the analogues of the YBa-free copperoxide. Our results suggest that the electronic structure of the symmetrically F-substituted or F-added compound is closer to that of the oxygen-deficient superconducting compound than that obtained from unsymmetrical substitution. This applies in particular if O is replaced with in an O(1) site. This suggests that superconductivity is very sensitive to the oxygen content of the $CuO_2$ layers.

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Full Geometry Optimizations of Bond-Stretch Isomers of C202+ Fullerene Dication by the Hybrid Density Functional B3LYP Methods

  • Lee, Ji-Hyun;Lee, Chang-Hoon;Park, Sung-S.;Lee, Kee-Hag
    • Bulletin of the Korean Chemical Society
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    • v.32 no.1
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    • pp.277-280
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    • 2011
  • We studied the relative stability and atomic structure of five $C_{20}^{2+}$ isomers obtained by two-electron ionization of a $C_{20}$ cage (the smallest fullerene). All the isomers are bond-stretch isomers, i.e., they differ in bond length. In particular, in one of the isomers with Ih symmetry, all the bond lengths are equal. Full geometry optimizations of the dipositive ion $C_{20}^{2+}$ were performed using the hybrid density functional (B3LYP/6-31G(d)) methods. All isomers were found to be true minima by frequency analysis at the level of B3LYP/6-31G(d) under the reinforced tight convergence criterion and a pruned (99,590) grid. The zero-point correction energy for the cage bond-stretch isomers was in the increasing order $D_{2h}<C_{2h}<C_2<T_h<I_h$ of $C_{20}^{2+}$. The energy difference among the isomers of cage dipositive ions was less than that among neutral cage isomers. Our results suggest that these isomers show bond-stretch isomerism and that they have an identical spin state and an identical potential energy curve. Although the predominant electronic configurations of the isomers are similar, the frontier orbital characteristics are different, implying that we could anticipate an entirely different set of characteristic chemical reactions for each type of HOMO and LUMO.

Bivalvation Valvuloplasty for Common Atrioventricular Valve Regurgitation in Functional Single Ventricle; Early and Mid-term Results (기능적 단심설에서 공통방실판 역류의 판막성형술; 판막 이분성형술(bivalvation)의 조기 및 중기 결과)

  • Chang, Yun-Hee;Sung, Si-Chan;Kim, Seon-Hee;Lee, Hyoung-Doo;Ban, Ji-Eun
    • Journal of Chest Surgery
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    • v.42 no.5
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    • pp.597-603
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    • 2009
  • Background: Atrioventricular valve regurgitation in pediatric patients with a functional single ventricles (FSV) - has been known as one of the important risk factors for death and unfavorable long-term results after a Fontan operation. We evaluated early and mid-term results of bivalvation valvuloplasty in FSV patients. Material and Method: We retrospectively evaluated 11 patients with a functional single ventricle who underwent bivalvationvalvuloplasty between 1999 and 2007. The degree of common atrioventricular valve regurgitation (CAVVR) was determined by color Doppler echocardiography (regurgitation grade scoring, trivial; 1, mild; 2, moderate; 3, severe; 4). Mean age at valve surgery was $6.9{\pm}7.0$ months (median 4 months, 24 days$\sim$21 months)and mean body weight was $6.2{\pm}2.8\;kg$ ($3.1{\sim}11.3\;kg$). Nine patients had isomerism heart and two of them had TAPVC. The concomitant procedures were performed in all but one patient. Additional commissural closure was performed in 3 patients and commissural annuloplasty in another 3 patients. Result: There was one hospital death after. surgery. A 32-day old patient who had been preoperatively dependent on a ventilator died of air way and lung problems 4.3 months after pulmonary artery banding and bivalvation valvuloplasty. Mean follow-up duration was 40 months ($4.3{\sim}114$ months). Mean preoperative CAVVR score was $3.3{\pm}0.6$, which decreased to $1.9{\pm}0.7$ postoperatively (p<0.0001). This residual regurgitation slightly increased to $2.2{\pm}0.4$ (no statistical significance) after a mean follow-up of 1.4.3 months. Six patients (60%) required re-operations for residual regurgitation at a subsequent bidirectionalcavopulmonary shunt or Fontan operation. One patient with Ebsteinoid malformation of the right sided atrioventricular valve required valve replacement due to stenoinsufficiency. Another patient required edge-to-edge repair at the right sided AV valve (between the right mural leaflet and the bridging leaflets). The remaining 4 patients required additional suture placements between bridging leaflets with or without commissural annuloplasty. All survivor had trivial or mild CAVVR at the latest follow-up. Conclusion: Bivalvation valvuloplasty for CAVVR in FSV patients is. an effective and safe procedure. However, significant numbers of the patients have small residual regurgitation and require additional valve procedures at subsequent operations. Long-term observations to monitor progression of the CAVVR is mandatory.