• Title/Summary/Keyword: Charge-transfer complex

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Crystal Structures of Bromine Sorption Complexes of $Ca^{2+}$-Exchanged Zeolite A

  • 장세복;송성환;김양
    • Bulletin of the Korean Chemical Society
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    • v.16 no.12
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    • pp.1163-1167
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    • 1995
  • The structures of dehydrated Ca4Na4-A (a=12.243(1) Å) and of its bromine sorption complex (a=12.214(1) Å) have been determined by single crystal x-ray diffraction techniques in the cubic space groupPm&bar{3}m at 21(1) ℃. Both crystals were dehydrated at 360 ℃ and 2 X 10-3 Torr for 2 days and one crystal was treated with 180 Torr of bromine vapor at 24 ℃ for 1 h. The structures were refined to final error indices, R1=0.066 and R2=0.078 with 192 reflections and R1=0.109 and R2=0.093 with 100 reflections, respectively, for which I>3σ(I). In these structures, four Ca2+ and four Na+ ions are located on two different threefold axes associated with 6-ring oxygens, respectively. In Ca4Na4-A·6Br2, four Ca2+ ions are recessed 0.28(1) Å into the large cavity and four Na+ ions extend 0.63(1) Å into the sodalite unit. A total of six dibromine molecules are sorbed per unit cell. Each Br2 molecule approaches a framework oxide ion axially with O(1)-Br(1)=3.27(2) Å Br(1)-Br(2)=2.66(6) Å and O(1)-Br(1)-Br(2)=172(1)°, indicating a charge-transfer interaction.

Electrocatalytic Effects for the Reduction of Thionyl Chloride in $Li/SOCl_2$ Cell Containing Schiff Base Metal(II) Complexes

  • Kim, Woo-Seong;Chung, Kwang-Il;Kim, Shin-Kook;Jeon, Seung-Won;Kim, Yeon-Hee;Sung, Yung-Eun;Choi, Yong-Kook
    • Bulletin of the Korean Chemical Society
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    • v.21 no.6
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    • pp.571-576
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    • 2000
  • Electrocatalytic effects for the reduction of thionyl chloride in $LiAICI_4/SOCl_2$ electrolyte solution containing Schiff base M(II) (M; Co and Fe) complexes are evaluated by determining kinetic parameters with cyclic voltammetry and chronoamperometry at a glassy carbon electrode. The charge transfer process during the reduction of thionyl chloride is affected by the concentration of the catalyst. The catalytic effects are demonstrated from both a shift of the reduction potential for the thionyl chloride toward a more positive direction and an increase in peak currents. Catalytic effects are larger in thionyl chloride solutions containing the binuclear [M(II) $_2$ (TSBP)] complex rather than mononuclear [M(II)(BSDT)] complexes. Significant improvements in the cell performance have been noted in terms of both thermodynamics and activation energy for the thionyl chloride reduction. The activation energy calculated from the Arrhenius plots is 4.5-5.9 kcal/mole at bare glassy carbon electrodes. The activation energy calculated for the catalyst containing solution is 3.3-4.9 kcalmole, depending on whether the temperature is lowered or rasied.

Synthesis and Characterization of Triptycene-Based Triphenylamine Electron Donor Molecules (트립티센 기반의 트리페닐아민 전자-주게 분자 합성 및 특성 분석)

  • Ryu, Youngjun;An, Byeong-Kwan
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.35 no.4
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    • pp.359-365
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    • 2022
  • The development of efficient electron donor (or hole-transporting) molecules that can be used in various optoelectronic device fields is highly demanded. In this work, a novel class of triptycene-based three-dimensional (3D) triphenylamine (TI-TPA) derivatives with different end substituents was designed and prepared for transparent electron donor materials. Owing to the rigid 3D triptycene framework, the obtained TI-TPA derivatives had an amorphous morphology with high thermal decomposition temperature. The oxidation potential of these TI-TPA derivatives decreased as the electron donating strength of the end substituent increased. Among TI-TPA derivatives, TI-TPA-OMe exhibited the highest HOMO level (-5.31 eV) which is similar to that of Spiro-OMeTAD (-5.22 eV). In addition, TI-TPA-OMe was found to form a strong charge transfer complex with the triptycene-based acceptor TI-BQ, leading to a new absorption band at around 640 nm. These results can be applied for developing efficient electron donor materials that can mimic the advantages of the spiro-linked structure and TPA units of Spiro-OMeTAD.

Synthesis and Characterization of Molybdeum Complexes with Schiff-Bases(II), Dioxobis(N-aryl-3-methoxysalicyaldiminato) Molybdenum(VI) Complexes (몰리브덴의 시프-염기착물의 합성과 그 성질 (제2보). 다이옥소비스(질소-아릴-3-메톡시살리실알디미나토)몰리브데늄(VI) 착물)

  • O, Sang O;Gu, Bon Gwon
    • Journal of the Korean Chemical Society
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    • v.29 no.3
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    • pp.257-264
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    • 1985
  • Dioxobis(3-methoxysalicyaldehydato)molybdeum(VI) complex has been synthesized by reactions of 3-methoxysalicylaldehyde and ammonium paramolybdate in methanol solution. With appropriate primary amine, the resulting complex gave schiff-base complexes, MoO$_2$(CH$_3$O-sal-N-R)$_2$ in which C=O oxide ligands had been replaced by nitrogen. The properties and possible molecular structure of these complexes were discussed by elemental analysis, spectroscopic studies and electric conductivities measurements. It was found that the Mo(VI) complexes contain a cis-MoO$_2$ group since their infrared spectra two Mo=O band at about 900cm$^{-1}$ and the combining ratios for MoO$_2$-ligand are 1 : 2. Also, electronic spectra of molybdenyl complexes assigned to ligand-to-metal charge transfer transition. All of these complexes are yellow or orange, depolar compound and slightly soluble in alcohol, dichloromethane, chloroform and N,N-dimethylformamide.

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Evaluation of Deterioration of Epoxy Primer for Steel Bridge Coating using Image Processing and Electrochemical Impedance Spectroscopy (화상처리 기법과 전기화학적 임피던스 분광법을 이용한 강교 도장용 에폭시 하도 도료의 열화 평가)

  • Lee, Chan Young;Lee, Sang Hun;Park, Jin Hwan
    • Corrosion Science and Technology
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    • v.8 no.2
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    • pp.53-61
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    • 2009
  • In this study, both evaluations by visual imaging for exterior view of coating and by EIS were executed for epoxy primer coated specimens deteriorated by accelerated test, and comparison and analysis were carried out for 2 evaluation methods. In the comparison between total damaged area ratio acquired by image processing method and deterioration point, higher deterioration points were appeared for rusted specimens than for non-rusted specimens. It is attributed that deterioration point per unit area ratio given for rust is higher than for peeling. In the comparison between total damaged area ratio and EIS result, impedance of coating was largely decreased as about TEX>$10^4{\Omega}{\cdot}cm^2$ or less when rust area ratio is more than about 0.1%, and blistering area ratio is more than about 3%. Charge transfer resistance ($R_{ct}$) and double layer capacitance ($C_{dl}$) values were appeared for all specimens except 2 ones, which shows that water is accumulated and steel substrate is corroded at coated film-steel interface. In the comparison between deterioration point and EIS result, more than 10 points as deterioration point were given for specimens of below $10^6{\Omega}{\cdot}cm^2$ of impedance at low frequency. For specimens deteriorated by NORSOK cyclic test, impedance was lowest of all, though deterioration point was not high. It is thought to be attributed that coating system and accelerated deterioration condition of cyclic tested specimens were different from those of main specimens. From the result, it is thought that coating resistance can be relatively more decreased than deterioration degree estimated from exterior view under more severe corrosion environment or in the present of more complex deterioration factors.

The Crystal Structure of an Iondine Sorption Complex of Dehydrated Calcium and Silver Exchanged Zeolite A ($Ag^+$이온과 $Ca^{2+}$이온으로 치환한 제올라이트 A를 탈수한 후 요오드를 흡착한 결정구조)

  • Bae, Myung-Nam;Kim, Yang;Kim, Un-Sik
    • Korean Journal of Crystallography
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    • v.6 no.2
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    • pp.118-124
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    • 1995
  • The crystal structure of an iodine sorption complex of vacumm-dehydrated Ag+ and Ca2+ exchanged zeolite A(a=12.174(3)Å) has been determined at 21℃ by single-crystal X-ray diffraction techniques in the cubic space group Pm3m. The crystal was prepared by flow method for three days using exchange solution in solution in which mole ratio of AgNO3 and Ca(NO3)2 was 1:150 with total concentration of 0.05 M. The complex was prepared by dehydration at 360℃ and 2×10-6 Torr for 2 days, followed by exposure to about 14.3 Torr of iodine vaporat 80℃ for 24 hours. Full-matrix least-squares refinement converged to the final error indices of R1=0.082, R2=0.068 using 122 reflections for which I > 3σ(I). Two Ag+ ions, 1.1 Ag+ ions, and 4.45 Ca2+ ions per unit cell are located on three different three-fold axes associated with 6-ring oxygens. Two Ag+ ions per unit cell are in the large cavity, 1.399(4)Å from the (111) plane of three oxygens. Another 1.1 Ag+ ions are found at opposite sites. Six iodine molecules are sorbed per unit cell. Each I2 molecule approaches a framework oxide ion axially (O-I=3.43(2)Å, I-I=2.92Å, I-I-O;166.1(3)°), by a charge transfer complex interaction. Two Ag+ ions make a close approach to the iodine molecules (Ag-I ; 2.73(2)Å).

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Preparation of Chitosan-Gold and Chitosan-Silver Nanodrug Carrier Using QDs (QDs를 이용한 키토산-골드와 키토산-실버 나노약물전달체 제조)

  • Lee, Yong-Choon;Kang, Ik-Joong
    • Korean Chemical Engineering Research
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    • v.54 no.2
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    • pp.200-205
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    • 2016
  • A drug transport carrier could be used for safe send of drugs to the affected region in a human body. The chitosan is adequate for the drug delivery carrier because of adaptable to living body. The gold, a metallic nanoparticles, tends to form a nano complex at rapidly when it combined with chitosan because of its negative charge. having energy from the other, outer gold nano-complex make heat due to its property to release the contained drugs to the target area. Silver could be also formed an useful biocompatible nano-composites with chitosan which should be used as an useful drug transfer carrier because its special ability to protect microbial contamination. Being one of the oxidized nano metals, $Fe_3O_4$ is nontoxic and has been used for its magnetic characteristics. In this study, the control of catalyst, reducing agent, and solvent amount. The chitosan-$Fe_3O_4$-gold & silver nanoshell have been changed to form about 100 nm size by ionic bond between the amine group, an end group of chitosan, and the metal. It was observed the change in order to seek for its optimum reaction condition as a drug transfer carrier.

Crystal Structures of Vacuum Dehydrated Fully $Cd^{2+}$-Exchanged Zeolite A and of Its iodine Sorption Complex (카드뮴 이온으로 완전히 치환한 제올라이트 A를 진공 탈수한 구조와 이것에 요오드를 흡착한 결정구조)

  • Jang, Se-Bok;Han, Young-Wook;Kim, Yang
    • Korean Journal of Crystallography
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    • v.4 no.2
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    • pp.54-62
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    • 1993
  • The crystal shnture of dehydrated fully Cd2+-exchanged zeolite A evacuated at 2 × 10-6 Torr and 650℃ (a:12.189(2) A) and of its iodine sorption corrplex (a:12.168(2)A) have been netsmlmn by single uystal x-ray diffraction techliques in the cubic space group hkTn at 21(1)℃. The strutures were refined to final error indices, Ri:0.057 and R2 =0.063 with 186 reflections and Rl:0.082 and R2:0.085 with 181 reflections, respectively, for which 1>3σ(In both structure, six lie at two distinguished threefold axes of unit cell ten the crystal structure of an iodine sorption complex of Cd6-A four Cd2+ ions are recessed 0.69(1) A into the large cavity to complex each with from the (111) plane of 0(3), whereas two Cd2+ ions recessed 0.68(1) A into the sodalite unit Awximately 4.0 l3ions per nit cell are sorbed. Each bridge between a Cd2+ ion and 8-ring oxygens ((I-I-I)= 117(1) ˚ and 0(1)-I(1)-I(2)=172(1)). The near linear I-I-0 angle and its interatomic distance (I-0=3.57(3) A) are indicative of a weak charge transfer interacticn between the frarrework oxygen and iodine. The existence of In3 inside the large cavity indicates that the If ions and H ions may be produced by reaction of In vapor with water molecules which maybe associated with Cd2+ ions in partially dehydrated Cd6-A In3- ions may be produced by the combination of I- and I2.

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Synthesis and Characterization of Metal Complex Oxo Vanadium(Ⅳ) Complexes with Derivatives of Salicylaldoximes (옥심계 금속착물의 합성과 그 물성에 관한 연구 치환 살리실알데히드옥심의 바나듐(Ⅳ) 착물(1))

  • Lee, Kwang;Lee, Won Sik
    • Journal of the Korean Chemical Society
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    • v.39 no.8
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    • pp.611-616
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    • 1995
  • Oxovanadium(IV) complexes with salicylaldoxime, o-vanilline oxime, 2-hydroxy-4-methoxybenzaldoxime, 2-hydroxy-5-methoxybenzaldoxime and 2-hydroxy-5-nitrobenzaldoxime were synthesized. The complexes have been characterized by elemental analysis, electric conductivity measurement, infrared spectrometry, electronic spectrometry, mass spectrometry, and thermal analysis. The results of elemental analysis were well coincided with the theoretical values. The values of molar conductance of the complexes in DMF implicated that the complexes were non-electrolyte. The characteristic stretching frequency of V=O appeared strong band in the range of $980{\pm}20\;cm^{-1}.$ All the complexes showed two d-d transition in visible spectra and two charge transfer transitions in ultraviolet spectra. Results of mass spectrometry of $VO(sal)_2\;and\;VO(van)_2$ indicated two peaks corresponding to vanadium containing ion(I) of 1 : 2(metal to ligand) chelate and a fragment ion(II) of 1 : 1 chelate due to loss of ligand radical from ion(I). The thermal analysis showed the endothermic peak due to the thermal decomposition.

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Physical Property and Morphology Observation of HepG2 Cells by Various Concentration of Paraquat (파라쿼트 농도에 따른 HepG2 세포의 물리적 특성 변화와 실시간 모폴로지 관찰)

  • Lee, Dong-Yun;Kang, Hyen-Wook;Muramatsu, Hiroshi;Kwon, Young-Soo
    • Proceedings of the KIEE Conference
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    • 2009.07a
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    • pp.1232_1233
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    • 2009
  • Paraquat is well-known to cause hepatotoxic responses in human and other mammal species. In solution, it forms free radicals and charge-transfer complex of which formation plays an important role in determination of its biological activity in the presence of various anions. The HepG2 cells were cultured onto a quartz crystal sensor which is possible to detect the density and a viscosity changes using the resonance frequency (F) and the resonance resistance (R). The plot of F-R diagram is able to explain the rheological change of cells onto the surface of the quartz crystal sensor. In this paper, we investigated the physical properties of the HepG2 cells cultured onto a ITO electrode of the quartz crystal sensor according to the paraquat injection at various concentrations (100 mM, 10 mM, 1 mM). We also observed the morphological changes with a micro CCD camera, simultaneously. The HepG2 cells were cultured onto the ITO electrode surface of the quartz crystal modified a collagen film in $CO_2$ incubator. After the paraquat injection, we observed the changes of the morphologies by the micro CCD camera depending on time and analyzed the physical changes of cells on the electrode surface of quartz crystal using F-R diagram. From all results, we proved the effect of paraquat at various concentrations which is led to an apoptosis such as weakening and death of the cells by oxidation and reduction reaction that were produced the superoxide anions and other free radicals.

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